Complex mixed ligand open framework materials

ABSTRACT

The disclosure provides multivariate metal organic frameworks comprising different functional ligands.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a U.S. National Stage Application filed under 35U.S.C. §371 based upon International Application No. PCT/US10/39154,filed Jun. 18, 2010, which application claims priority under 35 U.S.C.§119 from Provisional Application Serial Nos. 61/218,879, filed Jun. 19,2009 and 61/246,004, filed Sep. 25, 2009, the disclosures of which areincorporated herein by reference.

STATEMENT AS TO FEDERALLY SPONSORED RESEARCH

This invention was made with Government support of Grant No.W911NF-06-1-0405: P00001 awarded by the Department of Defense. The U.S.government has certain rights in this invention.

TECHNICAL FIELD

The disclosure provides organic frameworks for gas separation, storage,for use as sensors comprising mixed ligands.

BACKGROUND

Crystalline extended structures tend to be ‘simple’ in that they areconstructed from a small number of distinct building units.

SUMMARY

The structures of extended crystalline solids are fundamentally ‘simple’in that they are typically built from small number of distinct buildingunits. This is certainly the case in metal-organic frameworks (MOFs),where they are usually constructed from one kind of link, functionalityand metal ion unit.

The disclosure provides metal organic frameworks comprising a pluralityof different functional groups on a linking moiety or on at least twodifferent linking moieties. The porous organic framework ismulti-variant in that variations of the pore functionality can bereadily modified by incorporating at least two different functionalgroups into an organic framework. In one embodiment, the linking moietysubstructure is homogenous, however, a side-group on the linking moietyis varied.

The disclosure provides a porous organic framework comprising aplurality of linking moieties with different functional groups whoseorientation, number, relative position and ratio along the backbone arecontrollable by virtue of the unchanged size of the linking moiety andthe unaltered connectivity of the backbone and wherein the functionalgroups modify the chemical and physical properties of a pore in theframework. In one embodiment, the organic framework is constructed fromn different organic links, wherein n≧2. In another embodiment, thefunctional groups are along a core comprising a metal-oxide and phenylunits. In yet another embodiment, the organic framework comprisesrepeating units of metal-oxide joints and organic linking moieties, anda plurality of functional groups which are covalently bound to thelinking moieties, wherein the functional groups are heterogeneous and/orwherein the functional groups are differently spaced along a link. Inone embodiment, the organic framework comprises a MOF topologysubstantially identical to a MOF-5 framework. In another embodiment, theframework comprises a metal selected from the group consisting of: Li⁺,Na⁺, Rb⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Ti⁴⁺, Zr⁴⁺, Ta³⁺, Cr³⁺, Mo³⁺,W³⁺, Mn³⁺, Fe³⁺, Fe²⁺, Ru³⁺, Ru²⁺, Os³⁺, Os²⁺, Co³⁺, Co²⁺, Ni²⁺, Ni⁺,Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Au⁺, Zn²⁺, Al³⁺, Ga³⁺, In³⁺, Si⁴⁺,Si²⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Bi⁵⁺, Bi³⁺, and combinations thereof,along with corresponding metal salt counter-anions. In yet anotherembodiment, the linking moiety has a general structure selected from thegroup consisting of

wherein R₁-R₄ are selected from the group consisting of —H, —NH₂, —BR,—Cl, —NO₂, —CH₃, —OCH₂R₅, and —O—CH₂R₆, wherein R₅ is an alkyl or alkeneof from about 1-5 carbons, and R₆ is an aryl or substitute aryl, orwherein R₁-R₂ when adjacent can form a ring. In a further embodiment,the linking moiety comprises a member selected from the group consistingof:

In yet another embodiment, the organic framework comprises a firstlinking moiety of the plurality of linking moieties comprising a firstfunctional group and a second linking moiety of the plurality of linkingmoieties comprising a second functional group wherein the secondfunctional group can undergo post-synthesis reaction with apost-reactant group to further functionalize the framework. In yetanother embodiment the mvMOF comprises improved gas sorption capacitycompared to a framework having the same topology but homogenous linkingmoieties.

The disclosure also provides a method of making a mvMOF comprisingmixing a plurality of chemically functionalized linking moieties with ametal ion or metal nitrate, wherein the linking moieties are at adesired ratio to incorporate the desired ratio of a particularcombination of linking moieties into the organic framework, purifyingthe crystals and removing the solvent. In one specific embodiment, themethod comprises mixing a plurality of chemically functionalized linkingmoieties at desired ratios to incorporate the desired ratio of aparticular combination of linking moieties into an organic frameworkcomprising benzene dicarboxylic acids with zinc nitrate in DEF/DMF.

The disclosure also provides a gas separation device comprising anmvMOF. The disclosure also provides a gas storage device comprising anmvMOF.

The disclosure demonstrates in a specific embodiment a strategy formaking more complex MOFs by using links of multiple functionalities toproduce multivariate (MTV) structures. 1,4-benzenedicarboxylate (BDC, A)and its functionalized derivatives, —NH₂, —Br, —(Cl)₂, —NO₂, —(CH₃)₂,—C₄H₄, —(C₃H₅O)₂, and —(C₇H₇O)₂ (B-I, respectively), were used to buildeighteen mvMOFs, each of which has the cubic MOF-5 type crystalstructure and contains up to eight different functionalities (two:mvMOF-5-AB, -AC, -AD, -AE, -AF, -AG, -AH, -AI, -EI; three: mvMOF-5-ABC,-AHI, -EHI; four: mvMOF-5-ABCD, -ACEF; Five: mvMOF-5-ABCHI; six:mvMOF-5-ABCGHI; seven: mvMOF-5-ABCEGHI; eight: mvMOF-5-ABCEFGHI). Singlecrystal diffraction studies of a typical member of this series(mvMOF-5-ACEF) confirm that the MOF backbone (metal-oxide and phenylunits) is ordered and the functionalities are unavoidably disordered,which rules out the possibility of these MOFs being solid solutions.Nuclear magnetic resonance spectroscopy was used to determine thepresence of each functional group, their identity and ratio within thestructure of each member of the mvMOF series. These measurements werealso performed on several crystals selected from the solid products toconfirm their bulk homogeneity, and on segments of single crystals toconfirm the existence of an identical link ratio throughout the crystal.Although the latter observation may argue for a random distribution offunctionalities within the crystal, it is probably that they are morelikely to be arranged in a specific sequence because of link-linkinteractions which would inevitably create bias for a specific link at aspecific unhindered location. This is supported by the observedrelatively higher ratio of the least hindered link (A) in most of therespective mvMOFs. The ‘complex’ arrangement of functional groups withinthe pores results in up to 400% enhancement in the selectivity ofmvMOF-5-EHI for CO2 over CO compared to that of the same linkcounterpart (MOF-5).

The disclosure provide a complex self-assembled open framework materialconstructed from n (where n≧2) different organic links. This disclosureencompasses all open framework materials that are constructed fromorganic links bridged by multidentate organic or inorganic cores.Including all classes of open framework materials; covalent organicframeworks (COFs), zeolitic imidazolate frameworks (ZIFs) and metalorganic frameworks (MOFs) and all possible resulting net topologies asdescribed within the reticular chemistry structure resource(http:)//rcsr.anu.edu.au/ By utilizing greater than 2 links in theframework, complex architectures can be synthesized engenderingmultifarious materials. Such materials will have a variety of uses inapplication such as gas storage and separation and catalysis.

The details of one or more embodiments of the invention are set forth inthe accompanying drawings and the description below. Other features,objects, and advantages of the invention will be apparent from thedescription and drawings, and from the claims.

DESCRIPTION OF DRAWINGS

FIG. 1A-E shows a typical analysis performed on mvMOFs shown here forsamples of mvMOF-5-ABCD. (A) X-ray diffraction patterns of thecrystalline powder compared to the simulated one for MOF-5. (B)¹³CCP/MAS NMR spectrum showing unique resonance for each link. (C) Solution¹H NMR spectrum used to determine the ratio of links. (D) N₂ adsorptionisotherm at 77 K with adsorption and desorption points represented byclosed circles and open circles, respectively. (E) A large crystal fromwhich segments were analyzed for the ratio of links and found to beidentical throughout.

FIG. 2A-C shows (A) H₂ adsorption isotherm at 77 K of mvMOF-5-AH, -AI,-AHI and MOF-5. (B) CO₂ (circles) and CO (squares) adsorption isothermsat 298 K of mvMOF-5-EI, -EHI and MOF-5. Adsorption and desorptionbranches are represented by closed circles (squares for CO) and opencircles (squares for CO), respectively. (C) Plot of the percent ratio ofNH₂-BDC in MOF-5-AB determined by solution ¹H NMR versus thestoichiometric ratio used in the synthesis together with the tabulateddata of the molar ratio of NH₂-BDC versus BDC.

FIG. 3 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-AB (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 4 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-AC (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 5 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-AD (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 6 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-AE (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 7 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-AF (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 8 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-AG (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 9 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-AH (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 10 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-AI (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 11 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-EI (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 12 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-ABC (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 13 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-AHI (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 14 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-EHI (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 15 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-ABCD (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 16 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-ACEF (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 17 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-ABCHI (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 18 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-ABCGHI (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 19 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-ABCEGHI with the simulated MOF-5 diffraction pattern(bottom). The very high degree of correspondence between the patternsindicates that the bulk material has the same topology as MOF-5.

FIG. 20 shows a comparison of the experimental PXRD pattern ofas-prepared mvMOF-5-ABCEFGHI (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 21 is a TGA trace of activated mvMOF-5-AB.

FIG. 22 is a TGA trace of activated mvMOF-5-AC.

FIG. 23 is a TGA trace of activated mvMOF-5-AD.

FIG. 24 is a TGA trace of activated mvMOF-5-AE.

FIG. 25 is a TGA trace of activated mvMOF-5-AF.

FIG. 26 is a TGA trace of activated MOF-5-AG.

FIG. 27 is a TGA trace of activated mvMOF-5-AH.

FIG. 28 is a TGA trace of activated MOF-5-AI.

FIG. 29 is a TGA trace of activated mvMOF-5-EI.

FIG. 30 is a TGA trace of activated MOF-5-AHI.

FIG. 31 is a TGA trace of activated mvMOF-5-EHI.

FIG. 32 is a TGA trace of activated mvMOF-5-ACEF.

FIG. 33 is a TGA trace of activated mvMOF-5-ABCD.

FIG. 34 is a TGA trace of activated MOF-5-ABCEFGHI.

FIG. 35A-F are optical images. (A and B): Optical image ofas-synthesized mvMOF-5-AB-lsc. (C and D): Optical image ofas-synthesized mvMOF-5-ABCD-lsc. (E and F): Optical image ofas-synthesized mvMOF-5-ABCEFGHI-lsc.

FIG. 36 is a comparison of the experimental PXRD pattern of as-preparedsingle crystal of mvMOF-5-AB (top) with the simulated MOF-5 diffractionpattern (bottom). The very high degree of correspondence between thepatterns indicates that the bulk material has the same topology asMOF-5.

FIG. 37 is a comparison of the experimental PXRD pattern of as-preparedsingle crystal of mvMOF-5-ABCD (top) with the simulated MOF-5diffraction pattern (bottom). The very high degree of correspondencebetween the patterns indicates that the bulk material has the sametopology as MOF-5.

FIG. 38 is a comparison of the experimental PXRD pattern of as-preparedsingle crystal of mvMOF-5-ABCEFGHI (top) with the simulated MOF-5diffraction pattern (bottom). The very high degree of correspondencebetween the patterns indicates that the bulk material has the sametopology as MOF-5.

FIG. 39 is a comparison of the experimental PXRD pattern of as-preparedmvMOF-5-AB series (a-k) with the simulated MOF-5 diffraction pattern(black). The very high degree of correspondence between the patternsindicates that the bulk materials all have the same topology as MOF-5.

FIG. 40 is a plot of the percent ratio of B in mvMOF-5-AB seriesdetermined by solution ¹H NMR versus the stoichiometric ratio used inthe synthesis (top) together with optical image of the crystals showingthe color change from colorless to red (from left to right,respectively), mvMOF-5-AB-a to mvMOF-5-AB-k (bottom).

FIG. 41 is a comparison of the experimental PXRD pattern of as-preparedmvMOF-5-AI series (a-c) with the simulated MOF-5 diffraction pattern(black). The very high degree of correspondence between the patternsindicates that the bulk materials all have the same topology as MOF-5.

FIG. 42 is a comparison of the experimental PXRD pattern of as-preparedmvMOF-5-ABCD series (a-e) with the simulated MOF-5 diffraction pattern(black). The very high degree of correspondence between the patternsindicates that the bulk materials all have the same topology as MOF-5.

FIG. 43 shows an ORTEP drawing of a mvMOF-5-AC unit with both componentsof disordered groups shown, including hydrogen atoms and Br atoms. Znand O atoms were refined anisotropicly, while C and Br atoms wererefined isotropicly, and H atoms were put into the calculated position.All ellipsoids are displayed at the 15% probability level. Note that oneach phenyl ring, only one position is occupied by Br, out of all fourpositions as occupied by Br with equal possibility.

FIG. 44 shows an ORTEP drawing of a mvMOF-5-ACEF unit with allcomponents of the disordered groups shown (Br, CH₃, H). Only Zn wererefined anisotropicly, while O, C and Br atoms were refined isotropicly,and H atoms were put into the calculated position. All ellipsoids aredisplayed at the 15% probability level. Note that each phenyl ring canhave Br in one of four positions and a methyl group in two of fourpositions and that these can't co-exist. On this drawing, and in thestructure refinement, the constitution of NO₂, present in a very minoramount, has been neglected.

FIG. 45 shows nitrogen adsorption isotherms for mvMOF-5-AB (top), -ABCD(middle), and -ABCEFGHI (bottom) measured at 77 K. Filled and opensymbols represent adsorption and desorption branches, respectively.Connecting traces are guides for eye.

FIG. 46 shows argon adsorption isotherms for mvMOF-5 (top) andmvMOF-5-AI (bottom) measured at 87 K. Filled and open symbols representadsorption and desorption branches, respectively. Connecting traces areguides for eye.

FIG. 47 shows the calculated pore size distribution of mvMOF-5-AI-a andMOF-5 based on NLDFT model.

FIG. 48 shows nitrogen adsorption isotherms for MOF-5-AI-a (top),mvMOF-5-AI-b (middle) and mvMOF-5-AI-c measured at 77 K. Filled and opensymbols represent adsorption and desorption branches, respectively.Connecting traces are guides for eye.

FIG. 49 shows CO isotherms for MOF-5 taken at 273 (top), 283 (middle)and 298 K (bottom). Filled and open symbols represent adsorption anddesorption branches. Connecting traces are guides for eye.

FIG. 50 shows CO₂ isotherms for MOF-5 taken at 273 (top), 283 (middle)and 298 K (bottom). Filled and open symbols represent adsorption anddesorption branches. Connecting traces are guides for eye.

FIG. 51 shows CO isotherms for mvMOF-5-EI taken at 273 (top), 283(middle) and 298 K (bottom). Filled and open symbols representadsorption and desorption branches. Connecting traces are guides foreye.

FIG. 52 shows CO₂ isotherms for mvMOF-5-EI taken at 273 (top), 283(middle) and 298 K (bottom). Filled and open symbols representadsorption and desorption branches. Connecting traces are guides foreye.

FIG. 53 shows CO isotherms for mvMOF-5-EHI taken at 273 (top), 283(middle) and 298 K (bottom). Filled and open symbols representadsorption and desorption branches. Connecting traces are guides foreye.

FIG. 54 shows CO₂ isotherms for mvMOF-5-EHI taken at 273 (top), 283(middle) and 298 K (bottom). Filled and open symbols representadsorption and desorption branches. Connecting traces are guides foreye.

FIG. 55 depicts a cartoon showing variations for links making up mvMOFs.

FIG. 56 demonstrates multi-layered links used to generated mvMOFs aswell as examples of mvMOFs.

DETAILED DESCRIPTION

As used herein and in the appended claims, the singular forms “a,”“and,” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “a framework”includes a plurality of such frameworks and reference to “the metal”includes reference to one or more metals and equivalents thereof knownto those skilled in the art, and so forth.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood to one of ordinary skill inthe art to which this disclosure belongs. Although any methods andreagents similar or equivalent to those described herein can be used inthe practice of the disclosed methods and compositions, the exemplarymethods and materials are now described.

Also, the use of “or” means “and/or” unless stated otherwise. Similarly,“comprise,” “comprises,” “comprising” “include,” “includes,” and“including” are interchangeable and not intended to be limiting.

It is to be further understood that where descriptions of variousembodiments use the term “comprising,” those skilled in the art wouldunderstand that in some specific instances, an embodiment can bealternatively described using language “consisting essentially of” or“consisting of.”

All publications mentioned herein are incorporated herein by referencein full for the purpose of describing and disclosing the methodologies,which are described in the publications, which might be used inconnection with the description herein. The publications discussed aboveand throughout the text are provided solely for their disclosure priorto the filing date of the present application. Nothing herein is to beconstrued as an admission that the inventors are not entitled toantedate such disclosure by virtue of prior disclosure.

Crystalline extended structures tend to be ‘simple’ in that they areconstructed from a small number of distinct building units. Increasingthe number and diversity of such units provide the opportunity toimprove the properties of the crystalline structures. Indeed one canimagine developing artificial materials wherein a specific arrangementof a large number of different building units codes for a specificfunction or leads to a new phenomena. To date, crystalline materials ofthis kind of ‘complexity’ do not exist because their synthesis generallyyields either mixed phases, rather than a single phase of mixed units,or amorphous materials. Even in the well-established chemistry of blockcopolymers, slight changes in the functionality of the side chains leadto large undesirable changes in the polymer structure or to its phaseseparation; thus precluding expression of control over their structureand complexity.

Having developed methods of building rigid, ordered metal-organicframeworks (MOFs) in which metal-oxide units are linked by organicunits, the disclosure demonstrates that the inherent regularity of theMOF backbone could be useful in achieving controlled complexity intoMOFs. The disclosure demonstrates a strategy to introduce links withdifferent functional groups whose orientation, number, relative positionand ratio along the backbone are controllable by virtue of the unchangedsize of the link and the unaltered connectivity of the backbone. Such aMOF can be viewed as having a primary structure comprised of the‘simple’ repeating pattern of metal-oxide and organic link units, and a‘complex’ secondary structure formed by widely varied arrangements offunctional groups which are covalently bound to the links. In this way,each of the pores within the MOF would have an array of mixedfunctionalities pointing to their center. Accordingly, the sequence ofsuch functionalities and the frequency with which certain of them appearin the sequence will endow the pores with a new level of complexitywhich far exceeds any held by that of the original single-link MOFs; anaspect that allows fine-tuning of the pore environment with favorableimplications on properties.

The disclosure thus demonstrates that by combining the inherent rigidityof metal-organic frameworks (MOFs) and the functional flexibility ofpolymers, one can overcome these challenges and create a large number ofsingle phase materials each of which has multi-variate (MTV)functionalities.

The disclosure also provides methods of making multi-variate metalorganic frameworks (mvMOFs) by assembling their structures from linkswith different functional groups whose orientation, number, relativeposition and ratio, along the backbone (metal-oxide and phenyl units),can be controlled by virtue of the unchanged length of the link and itsunaltered connectivity (see FIG. 55). Accordingly, the sequence of suchfunctionalities and the frequency with which certain functional groupsappear in the sequence will endow the pores with a new level ofcomplexity which far exceeds any held by that of the original same-linkMOFs—an aspect that will allow fine-tuning of the pore environment withfavorable implications on properties.

The disclosure describes a general method for producing crystalline MOFmaterials which combine sets of two, three, four, five, six, seven,eight, nine, ten, eleven or twelve links of different functional groups,each of which is incorporated into a single structure where the ratio oflinks is controlled, and the material can be produced with bulk purity.The disclosure demonstrates the isolation of multi-variant MOFs as asingle phase. The porosity of mvMOFs is diverse and show thatmulti-varied links can introduce various functionalities. For example,varied links that can be introduced into a MOF structure include, butare not limited to, NO₂-BDC and (Cl)₂-BDC, into the MOF-5 type structure(mvMOF-5-AD and -AE), that otherwise do not form this structure whenused alone. The disclosure also demonstrates that members of this series(e.g, mvMOF-5-AHI and -EHI) show that the ‘whole is better than the sumof its parts’ as evidenced by the significant enhancement of gasadsorption and separation properties of the multi-varied link MOFscompared to their simple same-link analogues.

A multi-variant metal organic framework (mvMOF) refers to a MOFstructure comprising at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12different linking moieties having varied functionalities. The mvMOFcomprises a metal conjugated to a linking moiety via a linking cluster.The substructure of the linking moiety comprises different functionalityattributable by varying side-groups on the substructure. For example, anmvMOF comprises in cuboidal structure comprises at its corners metals(e.g., 4 metal atoms), each metal atom is conjugated to 3 linkingclusters, each linking cluster conjugated to a linking moietysubstructure. Accordingly, a cuboidal structure comprises 12 linkingmoieties. Variation in one or more side groups on the linking moietygenerates varied functionality of the resulting cuboidal structure.Taken to the size of a MOF framework, the variation in the frameworkprovides improved and diverse functions for gas storage, separation andpurification.

As used herein, a “core” refers to a repeating unit or units found in aframework. Such a framework can comprise a homogenous repeating core ora heterogeneous repeating core structure. A core comprises a transitionmetal or cluster of transitions metals and a linking moiety. A pluralityof cores linked together defines a framework.

The term “cluster” refers to identifiable associations of 2 or moreatoms. Such associations are typically established by some type ofbond—-ionic, covalent, Van der Waal, and the like.

A “linking cluster” refers to one or more reactive species capable ofcondensation comprising an atom capable of forming a bond between alinking moiety substructure and a metal group or between a linkingmoiety and another linking moiety. Examples of such species are selectedfrom the group consisting of a boron, oxygen, carbon, nitrogen, andphosphorous atom. In some embodiments, the linking cluster may compriseone or more different reactive species capable of forming a link with abridging oxygen atom. For example, a linking cluster can comprise CO₂H,CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₄,PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃, CH(RSH)₂, C(RSH)₃, CH(RNH₂)₂,C(RNH₂)₃, CH(ROH)₂, C(ROH)₃, CH(RCN)₂, C(RCN)₃, CH(SH)₂, C(SH)₃,CH(NH₂)₂, C(NH₂)₃, CH(OH)₂, C(OH)₃, CH(CN)₂, and C(CN)₃, wherein R is analkyl group having from 1 to 5 carbon atoms, or an aryl group comprising1 to 2 phenyl rings and CH(SH)₂, C(SH)₃, CH(NH₂)₂, C(NH₂)₃, CH(OH)₂,C(OH)₃, CH(CN)₂, and C(CN)₃. Typically linking clusters for bindingmetals in the generation of MOFs contain carboxylic acid functionalgroups.

The disclosure includes cycloalkyl or aryl substructures that comprise 1to 5 rings that consist either of all carbon or a mixture of carbon,with nitrogen, oxygen, sulfur, boron, phosphorous, silicon and aluminumatoms making up the ring.

The term “covalent organic polyhedra” refers to a non-extended covalentorganic network. Polymerization in such polyhedra does not occur usuallybecause of the presence of capping ligands that inhibit polymerization.Covalent organic polyhedra are covalent organic networks that comprise aplurality of linking moieties linking together multidentate cores suchthat the spatial structure of the network is a polyhedron. Typically,the polyhedra of this variation are 2 or 3 dimensional structures.

A “linking moiety” refers to a mono-dentate or polydentate compound thatbind a transition metal or a plurality of transition metals,respectively. Generally a linking moiety comprises a substructurecomprising an alkyl or cycloalkyl group, comprising 1 to 20 carbonatoms, an aryl group comprising 1 to 5 phenyl rings, or an alkyl or arylamine comprising alkyl or cycloalkyl groups having from 1 to 20 carbonatoms or aryl groups comprising 1 to 5 phenyl rings, and a linkingcluster at one or more positions of the substructure to facilitatecondensation with a metal. A cycloalkyl or aryl substructure maycomprise 1 to 5 rings that comprise either of all carbon or a mixture ofcarbon with nitrogen, oxygen, sulfur, boron, phosphorus, silicon and/oraluminum atoms making up the ring. Typically the linking moiety willcomprise a substructure having one or more carboxylic acid linkingclusters covalently attached. The substructure can be functionalizedwith reactive side groups.

As used herein, a line in a chemical formula with an atom on one end andnothing on the other end means that the formula refers to a chemicalfragment that is bonded to another entity on the end without an atomattached. Sometimes for emphasis, a wavy line will intersect the line.

In one aspect, the linking moiety substructure is selected from any ofthe following:

wherein R₁-R₄ are selected from the group consisting of —H, —NH₂, —BR,—Cl, —NO₂, —CH₃, —OCH₂R₅, and —O—CH₂R₆, wherein R₅ is an alkyl or alkeneof from about 1-5 carbons, and R₆ is an aryl or substitute aryl, orwherein R₁-R₂ when adjacent can form a ring. In one embodiment, thelinking ligand comprises a member selected from the group consisting of:

It is further contemplated that a mvMOF of the disclosure may begenerated by first utilizing a plurality of linking moieties havingdifferent functional groups, wherein at least one functional group maybe post-synthesis modified with a reacting group. In other words atleast one linking moiety comprises a function group that may bepost-synthesized reacted with a post framework reactant to furtherincrease the diversity of the functional groups in the organicframework.

In yet another embodiment, the linking moiety can have a generalstructure as set forth below:

wherein R₁-R₅ is H, NH₂, COOH, CN, NO₂, F, Cl, Br, I, S, O, SH, SO₃H,PO₃H₂, OH, CHO, CS₂H, SO₃H, Si(OH)₃, Ge(OH)₃, Sn(OH)₃, Si(SH)₄, Ge(SH)₄,PO₃H, AsO₃H, AsO₄H, P(SH)₃, As(SH)₃, CH(RSH)₂, C(RSH)₃, CHN(RNH₂)₂,C(RNH₂)₃, CH(ROH)₂, C(ROH)₃, CH(RCN)₂, C(RCN)₃,

wherein X=1, 2, or 3.

All the aforementioned linking moieties that possess appropriatereactive functionalities can be chemically transformed by a suitablereactant post framework synthesis to add further functionalities to thepores. By modifying the organic links within the frameworkpost-synthetically, access to functional groups that were previouslyinaccessible or accessible only through great difficulty and/or cost ispossible and facile. Post framework reactants include all known organictransformations and their respective reactants; rings of 1-20 carbonswith functional groups including atoms such as N, S, O. All metals thatmay chelate to and added functional group or a combination of previouslyexisting and newly added functional groups. All reactions that result intethering an organometallic complex to the framework for use, forexample, as a heterogeneous catalysts. Some examples of post frameworkreactants include:

wherein R=H, alkyl, aryl, OH, alkoxy, alkenes, alkynes, phenyl andsubstitutions of the foregoing, sulfur-containing groups (e.g.,thioalkoxy), silicon-containing groups, nitrogen-containing groups(e.g., amides), oxygen-containing groups (e.g., ketones and aldehydes),halogen, nitro, amino, cyano, boron-containing groups,phosphorus-containing groups, carboxylic acids or esters.

In addition, metal and metal containing compounds that may chelate toand add functional groups or a combination of previously existing andnewly added functional groups are also useful. Reactions that result inthe tethering of organometallic complexes to the framework for use as,for example, a heterogeneous catalyst can be used. Examples of postframework reactants include, but are not limited to, heterocycliccompounds.

In one embodiment, the post framework reactant can be a saturated orunsaturated heterocycle. The term “heterocycle” used alone or as asuffix or prefix, refers to a ring-containing structure or moleculehaving one or more multivalent heteroatoms, independently selected fromN, O and S, as a part of the ring structure and including at least 3 andup to about 20 atoms in the ring(s). Heterocycle may be saturated orunsaturated, containing one or more double bonds, and heterocycle maycontain more than one ring. When a heterocycle contains more than onering, the rings may be fused or unfused. Fused rings generally refer toat least two rings that share two atoms therebetween. A heterocycle mayhave aromatic character or may not have aromatic character. The terms“heterocyclic group”, “heterocyclic moiety”, “heterocyclic”, or“heterocyclo” used alone or as a suffix or prefix, refers to a radicalderived from a heterocycle by removing one or more hydrogens therefrom.The term “heterocyclyl” used alone or as a suffix or prefix, refers amonovalent radical derived from a heterocycle by removing one hydrogentherefrom. The term “heteroaryl” used alone or as a suffix or prefix,refers to a heterocyclyl having aromatic character. A heterocycleincludes, for example, a monocyclic heterocycle such as: aziridine,oxirane, thiirane, azetidine, oxetane, thietane, pyrrolidine, pyrroline,imidazolidine, pyrazolidine, pyrazoline, dioxolane, sulfolane2,3-dihydrofuran, 2,5-dihydrofuran tetrahydrofuran, thiophane,piperidine, 1,2,3,6-tetrahydro-pyridine, piperazine, morpholine,thiomorpholine, pyran, thiopyran, 2,3-dihydropyran, tetrahydropyran,1,4-dihydropyridine, 1,4-dioxane, 1,3-dioxane, dioxane, homopiperidine,2,3,4,7-tetrahydro-1H-azepine homopiperazine, 1,3-dioxepane,4,7-dihydro-1,3-dioxepin, and hexamethylene oxide.

In addition, a heterocycle includes aromatic heterocycles (heteroarylgroups), for example, pyridine, pyrazine, pyrimidine, pyridazine,thiophene, furan, furazan, pyrrole, imidazole, thiazole, oxazole,pyrazole, isothiazole, isoxazole, 1,2,3-triazole, tetrazole,1,2,3-thiadiazole, 1,2,3-oxadiazole, 1,2,4-triazole, 1,2,4-thiadiazole,1,2,4-oxadiazole, 1,3,4-triazole, 1,3,4-thiadiazole, and1,3,4-oxadiazole.

Additionally, heterocycle encompass polycyclic heterocycles, forexample, indole, indoline, isoindoline, quinoline, tetrahydroquinoline,isoquinoline, tetrahydroisoquinoline, 1,4-benzodioxan, coumarin,dihydrocoumarin, benzofuran, 2,3-dihydrobenzofuran, isobenzofuran,chromene, chroman, isochroman, xanthene, phenoxathiin, thianthrene,indolizine, isoindole, indazole, purine, phthalazine, naphthyridine,quinoxaline, quinazoline, cinnoline, pteridine, phenanthridine,perimidine, phenanthroline, phenazine, phenothiazine, phenoxazine,1,2-benzisoxazole, benzothiophene, benzoxazole, benzthiazole,benzimidazole, benztriazole, thioxanthine, carbazole, carboline,acridine, pyrolizidine, and quinolizidine.

In addition to the polycyclic heterocycles described above, heterocycleincludes polycyclic heterocycles wherein the ring fusion between two ormore rings includes more than one bond common to both rings and morethan two atoms common to both rings. Examples of such bridgedheterocycles include quinuclidine, diazabicyclo[2.2.1]heptane and7-oxabicyclo[2.2.1]heptane.

Heterocyclyl includes, for example, monocyclic heterocyclyls, such as:aziridinyl, oxiranyl, thiiranyl, azetidinyl, oxetanyl, thietanyl,pyrrolidinyl, pyrrolinyl, imidazolidinyl, pyrazolidinyl, pyrazolinyl,dioxolanyl, sulfolanyl, 2,3-dihydrofuranyl, 2,5-dihydrofuranyl,tetrahydrofuranyl, thiophanyl, piperidinyl,1,2,3,6-tetrahydro-pyridinyl, piperazinyl, morpholinyl, thiomorpholinyl,pyranyl, thiopyranyl, 2,3-dihydropyranyl, tetrahydropyranyl,1,4-dihydropyridinyl, 1,4-dioxanyl, 1,3-dioxanyl, dioxanyl,homopiperidinyl, 2,3,4,7-tetrahydro-1H-azepinyl, homopiperazinyl,1,3-dioxepanyl, 4,7-dihydro-1,3-dioxepinyl, and hexamethylene oxidyl.

In addition, heterocyclyl includes aromatic heterocyclyls or heteroaryl,for example, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl,furyl, furazanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, pyrazolyl,isothiazolyl, isoxazolyl, 1,2,3-triazolyl, tetrazolyl,1,2,3-thiadiazolyl, 1,2,3-oxadiazolyl, 1,2,4-triazolyl,1,2,4-thiadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-triazolyl,1,3,4-thiadiazolyl, and 1,3,4 oxadiazolyl.

Additionally, heterocyclyl encompasses polycyclic heterocyclyls(including both aromatic or non-aromatic), for example, indolyl,indolinyl, isoindolinyl, quinolinyl, tetrahydroquinolinyl,isoquinolinyl, tetrahydroisoquinolinyl, 1,4-benzodioxanyl, coumarinyl,dihydrocoumarinyl, benzofuranyl, 2,3-dihydrobenzofuranyl,isobenzofuranyl, chromenyl, chromanyl, isochromanyl, xanthenyl,phenoxathiinyl, thianthrenyl, indolizinyl, isoindolyl, indazolyl,purinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl,cinnolinyl, pteridinyl, phenanthridinyl, perimidinyl, phenanthrolinyl,phenazinyl, phenothiazinyl, phenoxazinyl, 1,2-benzisoxazolyl,benzothiophenyl, benzoxazolyl, benzthiazolyl, benzimidazolyl,benztriazolyl, thioxanthinyl, carbazolyl, carbolinyl, acridinyl,pyrolizidinyl, and quinolizidinyl.

In addition to the polycyclic heterocyclyls described above,heterocyclyl includes polycyclic heterocyclyls wherein the ring fusionbetween two or more rings includes more than one bond common to bothrings and more than two atoms common to both rings. Examples of suchbridged heterocycles include quinuclidinyl, diazabicyclo[2.2.1]heptyl;and 7-oxabicyclo[2.2.1]heptyl.

Metal ions that can be used in the synthesis of frameworks of thedisclosure include Li⁺, Na⁺, Rb⁺, Mg⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Ti⁴⁺,Zr⁴⁺, Ta³⁺, Cr³⁺, Mo³⁺, W³⁺, Mn³⁺, Fe³⁺, Fe²⁺, Ru³⁺, Ru²⁺, Os³⁺, Os²⁺,CO³⁺, CO²⁺, Ni²⁺, Ni⁺, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Au⁺, Zn²⁺, Al³⁺,Ga³⁺, In³⁺, Si⁴⁺, Si²⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Bi⁵⁺, Bi³⁺, andcombinations thereof, along with corresponding metal saltcounter-anions.

The disclosure also provides a method of making a mvMOF of thedisclosure. The methods comprises mixing a plurality of chemicallyfunctionalized linking moieties at desired ratios to incorporate thedesired ratio of a particular combination of linking moieties into anorganic framework with a metal ion or metal-nitrate in an appropriatebuffer. The resultant crystalline material is then purified and thesolvent removed. In one embodiment, the method comprises mixing aplurality of chemically functionalized linking moieties at desiredratios to incorporate the desired ratio of a particular combination oflinking moieties into an organic framework comprising benzenedicarboxylic acids with zinc nitrate in DEF/DMF at 85-100° C. for 24-48h. The resultant crystalline material is then immersed in DMF for 24 hand then sequentially in chloroform for three 24 h periods. Finally,this porous material is activated by removing the solvent under vacuumfor 24 h at room temperature or heat up to 120° C.

The preparation of the frameworks of the disclosure can be carried outin either an aqueous or non-aqueous system. The solvent may be polar ornon-polar as the case may be. The solvent can comprise the templatingagent or the optional ligand containing a monodentate functional group.Examples of non-aqueous solvents include n-alkanes, such as pentane,hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene,cyanobenzene, aniline, naphthalene, naphthas, n-alcohols such asmethanol, ethanol, n-propanol, isopropanol, acetone,1,3,-dichloroethane, methylene chloride, chloroform, carbontetrachloride, tetrahydrofuran, dimethylformamide, dimethylsulfoxide,N-methylpyrollidone, dimethylacetamide, diethylformamide, thiophene,pyridine, ethanolamine, triethylamine, ethlenediamine, and the like.Those skilled in the art will be readily able to determine anappropriate solvent based on the starting reactants and the choice ofsolvent is not believed to be crucial in obtaining the materials of thedisclosure.

Templating agents can be used in the methods of the disclosure.Templating agents employed in the disclosure are added to the reactionmixture for the purpose of occupying the pores in the resultingcrystalline base frameworks. In some variations of the disclosure,space-filling agents, adsorbed chemical species and guest speciesincrease the surface area of the metal-organic framework. Suitablespace-filling agents include, for example, a component selected from thegroup consisting of: (i) alkyl amines and their corresponding alkylammonium salts, containing linear, branched, or cyclic aliphatic groups,having from 1 to 20 carbon atoms; (ii) aryl amines and theircorresponding aryl ammonium salts having from 1 to 5 phenyl rings; (iii)alkyl phosphonium salts, containing linear, branched, or cyclicaliphatic groups, having from 1 to 20 carbon atoms; (iv) arylphosphonium salts, having from 1 to 5 phenyl rings; (v) alkyl organicacids and their corresponding salts, containing linear, branched, orcyclic aliphatic groups, having from 1 to 20 carbon atoms; (vi) arylorganic acids and their corresponding salts, having from 1 to 5 phenylrings; (vii) aliphatic alcohols, containing linear, branched, or cyclicaliphatic groups, having from 1 to 20 carbon atoms; or (viii) arylalcohols having from 1 to 5 phenyl rings.

Crystallization can be carried out by leaving the solution at roomtemperature or in isothermal oven for up to 300° C.; adding a dilutedbase to the solution to initiate the crystallization; diffusing adiluted base into the solution to initiate the crystallization; and/ortransferring the solution to a closed vessel and heating to apredetermined temperature.

Also provided are devices for the sorptive uptake of a chemical species.The device includes a sorbent comprising a framework provided herein orobtained by the methods of the disclosure. The uptake can be reversibleor non-reversible.

In some embodiments, the sorbent is included in discrete sorptiveparticles. The sorptive particles may be embedded into or fixed to asolid liquid- and/or gas-permeable three-dimensional support. In someembodiments, the sorptive particles have pores for the reversible uptakeor storage of liquids or gases and wherein the sorptive particles canreversibly adsorb or absorb the liquid or gas.

In some embodiments, a device provided herein comprises a storage unitfor the storage of chemical species such as ammonia, carbon dioxide,carbon monoxide, hydrogen, amines, methane, oxygen, argon, nitrogen,argon, organic dyes, polycyclic organic molecules, and combinationsthereof.

Also provided are methods for the sorptive uptake of a chemical species.The method includes contacting the chemical species with a sorbent thatcomprises a framework provided herein. The uptake of the chemicalspecies may include storage of the chemical species. In some aspects,the chemical species is stored under conditions suitable for use as anenergy source.

Natural gas is an important fuel gas and it is used extensively as abasic raw material in the petrochemical and other chemical processindustries. The composition of natural gas varies widely from field tofield. Many natural gas reservoirs contain relatively low percentages ofhydrocarbons (less than 40%, for example) and high percentages of acidgases, principally carbon dioxide, but also hydrogen sulfide, carbonylsulfide, carbon disulfide and various mercaptans. Removal of acid gasesfrom natural gas produced in remote locations is desirable to provideconditioned or sweet, dry natural gas either for delivery to a pipeline,natural gas liquids recovery, helium recovery, conversion to liquefiednatural gas (LNG), or for subsequent nitrogen rejection. CO₂ iscorrosive in the presence of water, and it can form dry ice, hydratesand can cause freeze-up problems in pipelines and in cryogenic equipmentoften used in processing natural gas. Also, by not contributing to theheating value, CO₂ merely adds to the cost of gas transmission.

An important aspect of any natural gas treating process is economics.Natural gas is typically treated in high volumes, making even slightdifferences in capital and operating costs of the treating unitsignificant factors in the selection of process technology. Some naturalgas resources are now uneconomical to produce because of processingcosts. There is a continuing need for improved natural gas treatingprocesses that have high reliability and represent simplicity ofoperation.

In addition, removal of carbon dioxide from the flue exhaust of powerplants, currently a major source of anthropogenic carbon dioxide, iscommonly accomplished by chilling and pressurizing the exhaust or bypassing the fumes through a fluidized bed of aqueous amine solution,both of which are costly and inefficient. Other methods based onchemisorption of carbon dioxide on oxide surfaces or adsorption withinporous silicates, carbon, and membranes have been pursued as means forcarbon dioxide uptake. However, in order for an effective adsorptionmedium to have long term viability in carbon dioxide removal it shouldcombine two features: (i) a periodic structure for which carbon dioxideuptake and release is fully reversible, and (ii) a flexibility withwhich chemical functionalization and molecular level fine-tuning can beachieved for optimized uptake capacities.

A number of processes for the recovery or removal of carbon dioxide fromgas steams have been proposed and practiced on a commercial scale. Theprocesses vary widely, but generally involve some form of solventabsorption, adsorption on a porous adsorbent, distillation, or diffusionthrough a semipermeable membrane.

The following examples are intended to illustrate but not limit thedisclosure. While they are typical of those that might be used, otherprocedures known to those skilled in the art may alternatively be used.

EXAMPLES

The following examples are exemplary only and are not intended to limitthe diversity of the MOF structures that may be modified to includevarious ligands and functional groups. In one embodiment, the cubicMOF-5 structure was used and combined with the acid form of1,4-benzenedicarboxylate (BDC), NH₂-BDC, Br-BDC, (Cl)₂-BDC, NO₂-BDC,(CH₃)₂-BDC, C₄H₄-BDC, (C₃H₅O)₂-BDC, and (C₇H₇O)₂-BDC links (FIG. 56—A-I, respectively) to form the corresponding sets of eighteen mvMOFseach having two or more different functionalities (two: mvMOF-5-AB, -AC,-AD, -AE, -AF, -AG, -AH, -AI, -EI; three: mvMOF-5-ABC, -AHI, -EHI; four:mvMOF-5-ABCD, -ACEF; Five: mvMOF-5-ABCHI; six: mvMOF-5-ABCGHI; seven:mvMOF-5-ABCEGHI; eight: mvMOF-5-ABCEFGHI, FIG. 56). The disclosuredemonstrates the isolation as single phases, the structure of MOF-5backbone, and their porosity, and show that this multi-varied linksynthetic strategy is useful in introducing functionalities, such asNO₂-BDC and (Cl)₂-BDC, into the MOF-5 type structure (mvMOF-5-AD and-AE), that otherwise do not form this structure when used alone. Thedata also demonstrate that members of this series (mvMOF-5-AHI and -EHI)show that the ‘whole is better than the sum of its parts’ as evidencedby the significant enhancement of gas adsorption and separationproperties of the multi-varied link MOFs compared to their simplesame-link analogues.

Crystals of mvMOFs were obtained by adding Zn(NO₃)₂.4H₂O to aN,N-dimethylformamide (DMF) solution mixture of the acid form of theselected organic links under conditions previously used in the synthesisof MOF-5. All the compounds were characterized by powder X-raydiffraction (PXRD), ¹³C cross polarization magic angle spinning (CP/MAS)NMR, ¹H NMR on acid-digested solutions of their crystals, andthermogravimetric analysis (TGA), to assess their crystallinity, linkcomposition, link ratio, and thermal stability, respectively. Theporosity of a subset of these compounds (all containing two, three, orfour different links, and mvMOF-5-ABCEFGHI) was evaluated by nitrogengas adsorption measurements. Although the complete characterizationprocedure and the data acquired on all the compounds was performed, theparticulars of mvMOF-5-ABCD is provided as an illustrative example.

The compound was synthesized from equimolar amounts of link A, B, C andD (as set forth in FIG. 56). Its high crystallinity was evident from thePXRD pattern of the as-synthesized samples which gave sharp diffractionlines matching those of the parent MOF-5 structure (FIG. 1A). In orderto determine the ratio of the four types of link in mvMOF-5-ABCD, thesample was evacuated by heating at 50° C. under vacuum (10 mTorr) for 24hours to remove any guest solvent molecules from the pores that wereoccluded during synthesis. TGA performed on this sample showed no weightloss up to 400° C., confirming that all guest molecules were removedfrom the pores and that the evacuated framework is thermally stable.

¹³C CP/MAS NMR spectra of evacuated samples of mvMOF-5-ABCD showedresonances at 150.3, 127.0, 133.7 and 136.3 ppm which are characteristicof the unique carbon atoms of NH₂-BDC, Br-BDC, (Cl)₂-BDC and BDC links,respectively (FIG. 1B). These spectra clearly indicate their presence inthe MOF backbone. Additionally, the same experiment was performed on amixture of the constituent free links of mvMOF-5-ABCD, where a distinctshift of 2 ppm was observed between the carbonyl carbons of the freelinks and those of the links that are incorporated into the framework,thus confirming that no unbound organic link is present within the MOFcrystals. Similar analyses on all the remaining mvMOFs led to the sameconclusion.

The precise link ratio was obtained from the ¹H NMR spectra of a DCldigested solution of the mvMOF-5-ABCD solid (Table 1, Link Composition).Resonances with the predicted coupling patterns were observed in theexpected regions for each of the unique protons of the links (FIG. 1C).By integrating resonance peak intensities, the links are demonstrated tobe present in the MOF in the proportion 1.00:0.12:0.56:0.40,respectively. To show that these ratios are the same in the crystal asin the bulk solid, the solution ¹H NMR experiments discussed above wereperformed on 4 different crystals randomly selected from themvMOF-5-ABCD bulk sample, and showed that the ratios are nearlyidentical. The same experiment was also performed on mvMOF-5-AB, and-ABCEFGHI, again confirming the bulk homogeneity of the mvMOF series(Table 1, Bulk Homogeneity). Furthermore the porosity and architecturalstability of the original MOF-5 structure are preserved in the mvMOFcompounds as illustrated by the Type I nitrogen adsorption isotherm,shown in FIG. 1D for mvMOF-5-ABCD, and its high surface area (2860 m²g⁻¹). In addition, by synthesizing mvMOF-ABCD, from a variety of linkmolar ratios the data demonstrated that, in a given mvMOF, the linkratio can be controlled by modifying the reaction stoichiometry (Table1, Control of Link Ratio). In essence, this type of control in linkratios translates into control of the population and diversity offunctional groups pointing into the pores without altering theunderlying connectivity of the primary structure as evidenced by theirpreserved PXRD patterns (FIG. 28).

X-ray crystallographic studies performed on single crystals ofmvMOF-5-AC and -ACEF revealed, as expected, an ordered cubic MOF-5structure composed of rigid phenyl units joined by Zn₄O(CO₂)₆ vertices.The non-hydrogen atoms of the functional groups on the phenyl units inthese materials are all present at very low occupancy. Each functionalgroup is required by symmetry to be disordered over two (dimethyl groupsof link F) or four (Br group of link C, or nitro group of link E)positions because of an equal probability of their location on the fourcarbon atoms of the phenyl ring. Br in mvMOF-5-AC can be refined despiteits low occupancy and the low contribution to the intensity of the data.In mvMOF-5-ACEF, the occupancies of functional group atoms are alsoquite low; however, because there is overlap of the positions of Br(link C), N (link E) and C (link F) atoms the difference peak could belocated. Given that phenyl unit atoms are present in all mvMOFs, all ofthese parameters were successfully refined for the backbone non-hydrogenatoms. This clearly indicates that the structures of mvMOFs are notsolid solutions but rather they represent a system of varied functionalgroups covalently linked to an ordered framework.

Given the uniqueness of the mvMOFs' construct, a significant questionthat arises is whether the crystals are comprised of macroscopic domainsof functionalities, or distinct sequences of functional units repeatedthroughout the framework backbone. To distinguish these twopossibilities large single crystals were prepared of mvMOF-5-AB, -ABCD(FIG. 1E) and -ABCEFGHI of dimensions of 4.0×4.0×2.0 mm, 2.0×2.0×2.0 mmand 2.0×2.0×1.0 mm, respectively. In each case the structure of eachsingle crystal was confirmed by its PXRD pattern (FIG. 24-26). Eachcrystal was dissected into three equal segments and then the solution ¹HNMR spectra were collected on acid digested samples of each segment ofeach crystal, respectively. If macroscopic domains of homogeneous linkswere present within a single crystal of the mvMOF, a different linkratio would be expected for each of the three segments of the respectiveparent crystal. However, the data clearly show that the linkdistribution ratios are identical for each segment of the three mvMOFsstudied (Table 1, Segments of Single Crystals), thus suggesting theabsence of macroscopic domains. Further evidence supporting thisconclusion is the absence of a narrow pore size distribution formvMOF-5-AI as one would observe for MOF-5 or any other same-link MOF,which suggests that link I is distributed throughout the pores. Thisdoes not preclude the presence of microscopic domains where one mightexpect the dominance of a specific functionality (or a subset offunctionalities) over the nanometer scale.

TABLE 1 Ratio of links found in mvMOF crystals (bold) compared to theadded ratio. Numerical value of link A was normalized to 1 in each case.Compound A, A B, B C, C D, D E, E F, F G, G H, H I, I Link compositionMTV-MOF-5-AB 1.0, 1 0.57, 1 MTV-MOF-5-AC 1.0, 1 0.61, 1 MTV-MOF-S-AD1.0, 1 0.63, 1 MTV-MOF-5-AE 1.0, 1 0.40, 1 MTV-MOF-5-AF 1.0, 1 1.24, 1MTV-MOF-5-AG 1.0, 1 0.52, 1 MTV-MOF-5-AH 1.0, 1 0.46, 1 MTV-MOF-5-AI1.0, 1 0.40, 1 MTV-MOF-5-EI* 0.20, 1   1, 1 MTV-MOF-5-ABC 1.0, 1 0.052,1  0.52, 1 MTV-MOF-F-AHI 1.0, 1 0.48, 1 0.50, 1 MTV-MOF-5-EHI* 0.62, 10.89, 1   1, 1 MTV-MOF-5-ABCD 1.0, 1 0.12, 1 0.56, 1 0.40, 1MTV-MOF-5-ACEF 1.0, 1 0.49, 1 0.22, 1 0.62, 1 MTV-MOF-5-ABCHI 1.0, 10.017, 1  0.22, 1 0.62, 1 0.32, 1 MTV-MOF-5-ABCGHI 1.0, 1 0.093, 1 0.87, 1 0.67, 1 0.73, 1 0.80, 1 MTV-MOF-5-ABCEGHI 1.0, 1 0.077, 1   1.0,1 0.69, 1 0.77, 1 0.73, 1 0.96, 1 MTV-MOF-5-ABCEFGHI 1.0, 1 0.14, 10.56, 1 0.29, 1 0.67, 1 0.56, 1 0.48, 1 0.56, 1 Bulk HomogeneityMTV-MOF-5-AB set 1 1.0, 1 0.58, 1 MTV-MOF-5-AB set 2 1.0, 1 0.58, 1MTV-MOF-5-AB set 3 1.0, 1 0.57, 1 MTV-MOF-5-ABCD set 1 1.0, 1 0.12, 10.59, 1 0.39, 1 MTV-MOF-5-ABCD set 2 1.0, 1 0.11, 1 0.56, 1 0.38, 1MTV-MOF-5-ABCD set 3 1.0, 1 0.11, 1 0.53, 1 0.36, 1 MTV-MOF-5-ABCEFGHIset 1 1.0, 1 0.12, 1 0.56, 1 0.28, 1 0.67, 1 0.56, 1 0.48, 1 0.54, 1MTV-MOF-5-ABCEFGHI set 2 1.0, 1 0.12, 1 0.56, 1 0.28, 1 0.67, 1 0.56, 10.51, 1 0.56, 1 MTV-MOF-5-ABCEFGHI set 3 1.0, 1 0.14, 1 0.56, 1 0.29, 10.67, 1 0.56, 1 0.48, 1 0.54, 1 Control of Link Ratio MTV-MOF-5-ABCD-a1.0, 1 0.12, 1 0.56, 1 0.40, 1 MTV-MOF-5-ABCD-b  1.0, 0.5 0.26, 1 1.24,1  1.99, 1.5 MTV-MOF-5-ABCD-c  1.0, 1.5 0.06, 1 0.43, 1  0.30, 0.5MTV-MOF-5-ABCD-d 1.0, 1  0.32, 1.5  0.26, 0.5 0.44, 1 MTV-MOF-5-ABCD-e1.0, 1  0.03, 0.5   1.0, 1.5 0.67, 1 Segments of a Single CrystalMTV-MOF-5-AB segment 1 1.0, 1 0.57, 1 MTV-MOF-5-AB segment 2 1.0, 10.58, 1 MTV-MOF-5-AB segment 3 1.0, 1 0.54, 1 MTV-MOF-5-ABCD segment 11.0, 1 0.10, 1 0.48, 1 0.31, 1 MTV-MOF-5-ABCD segment 2 1.0, 1 0.11, 10.50, 1 0.31, 1 MTV-MOF-5-ABCD segment 3 1.0, 1 0.11, 1 0.51, 1 0.34, 1MTV-MOF-5-ABCEFGHI segment 1 1.0, 1 0.05, 1 0.52, 1 0.15, 1 0.46, 10.48, 1 0.42, 1 0.57, 1 MTV-MOF-5-ABCEFGHI segment 2 1.0, 1 0.06, 10.53, 1 0.15, 1 0.48, 1 0.49, 1 0.45, 1 0.59, 1 MTV-MOF-5-ABCEFGHIsegment 3 1.0, 1 0.05, 1 0.50, 1 0.14, 1 0.45, 1 0.47, 1 0.40, 1 0.58, 1*Numerical value of link E was normalized to 1.

The possible presence of distinct sequences of functionalities along theMOF backbone would inevitably lead to a complex pore environment andprovide opportunities for uncovering unusual properties. Since same-linkMOF-5 structure is known to take up a significant amount of gases (e.g.,H₂, CO₂), the mvMOFs were tested in these applications, and to determinewhether their performance is greater than that of their constituents. InFIG. 2A, a comparison between the H₂ storage capacities of mvMOF-5-AHI,-AH, -HI and MOF-5 is shown. Remarkably, the isotherms clearlydemonstrate that the uptake capacity of mvMOF-5-AHI is greater than thatof mvMOF-5-AH, -HI and -A (MOF-5) by a maximum of 84%. Similarly, anunusual increase in the selective uptake capacity of CO₂ over CO wasobserved: 400% better selectivity in the case of mvMOF-5-EHI for CO₂compared to MOF-5 (FIG. 2B).

These findings demonstrate that the properties of mvMOFs are not simplelinear combinations of their constituents, thus supporting the notionthat the sequence of functionalities within mvMOF can be useful as codefor the enhancement of a specific property or achieving a new property.

Detailed synthetic procedures for the preparation of mvMOF includingmulti-gram scale products, and experimental and simulated PXRD patterns.

Terephthalic acid (Benzene-1,4-dicaboxylic acid or BDCH₂),2-aminoterephthalic acid (NH₂-BDCH₂), 2-bromoterephthalic acid(Br-BDCH₂), 2,5-dichloroterephthalic acid ((Cl)₂-BDCH₂),2-nitroterephthalic acid (NO₂-BDCH₂), naphthalene-1,4-dicarboxylic acid(C₄H₄-BDCH₂) were purchased from the Aldrich Chemical Co.N,N-dimethylformamide (DMF) is purchased from the Fisher ScientificInternational Inc. Zinc nitrate tetrahydrate Zn(NO₃)₂.4H₂O was purchasedfrom EM Science. 2,5-dimethylterephthalic acid ((CH₃)₂-BDCH₂) waspurchased from TCI America. All starting materials above were usedwithout further purification. N,N-diethylformamide (DEF, BASF) solventwas purified by filtration through a column filled with activated carbon(Calgon) and silica gel (EMD, silica gel 60), and chloroform (Fisher,HPLC grade, pentene stabilized) was dried over freshly activatedmolecular sieves 4A prior to use. 2,5-Bis(allyloxy)terephthalic acid((C₃H₅O)2-BDCH₂), 2,5-bis(benzyloxy)terephthalic acid ((C₇H₇O)₂-BDCH₂)were synthesized.

Multi-variate metal-organic framework (mvMOFs) are synthesized by mixingvaried amounts of chemically functionalized benzene dicarboxylic acidswith zinc nitrate in DEF/DMF at 85-100° C. for 24-48 h. The resultantcrystalline material is then immersed in DMF for 24 h and thensequentially in chloroform for three 24 h periods. Finally, this porousmaterial is activated by removing the solvent under vacuum for 24 h atroom temperature or heat up to 120° C.

In order to precisely control the amount of starting material, asolution of teraphthalic acid link in DMF/DEF (0.025-0.10 M (1 M=1 moldm⁻³)) and a solution of zinc nitrate tetrahydrate in DMF/DEF (0.10 M)were used as stock solutions. DMF and DEF have been chosen as thesolvents of synthesis due to their high boiling points, which aresuitable for the solvothermal synthesis. A lower boiling solvent mayresult in the precipitation of the reactants rather than of the product.After reaction, the crystals were examined under optical microscope,collected, and characterized by powder X-ray diffraction (PXRD). PXRDdata of a crushed large single cubic crystal was recorded on a BrukerAXS D8 Advance diffractometer operated at 40 kV, 40 mA for Cu Kα,(λ=1.5406 Å) with a scan speed of 3°/min and a step size of 0.050° in26. Simulated MOF-5 PXRD pattern was calculated using software PowderCell v.2.2 from the single crystal structure published earlier.

¹H NMR of digested mvMOFs: In general, 8 mg of dried (or solventexchanged with DMF) mvMOF was digested and dissolved with sonication in1.0 mL dilute DCl solution (prepared from 200 μL of 20% DCl/D₂O solution(Aldrich) and 10 mL DMSO-d6). The digestion solution was used directlyfor ¹H-NMR.

Synthesis of mvMOFs: mvMOF-5-AB, Zn₄O(BDC)1.92(NH₂-BDC)1.08: 0.10 mL ofBDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mL of NH₂-BDCH₂ stocksolution (0.10 M, 1.0×10⁻⁵ mol), 0.20 mL of Zn(NO₃)₂.4H₂O stock solution(0.30 M, 6.0×10-5 mol) and 0.60 mL of DEF were added in sequence in to a4 mL glass vial. The vial was sealed and heated in an isothermal oven at100° C. and allowed to react solvothermally for 48 h. The product was inthe form of cubic shaped brown single crystals. PXRD was checked, itmatches the simulated MOF-5 powder diffraction pattern (FIG. 4).

¹H NMR of the digested mvMOF-5-AB crystals (400 MHz, DMSO-d6). BDCH₂ δ:8.00 (s, 4H). NH₂-BDCH₂ δ: 7.03 (d, 1H), 7.38 (s, 1H), 7.74 (d, 1H).Molar ratio based on integration of the peaks: BDC:NH₂-BDC=1:0.57.

mvMOF-5-AC, Zn₄O(BDC)_(1.86)(Br-BDC)_(1.14):

0.10 mL of Br-BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mL ofBDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.20 mL of Zn(NO₃)₂.4H₂Ostock solution (0.30 M, 6.0×10⁻⁵ mol) and 0.60 mL of DEF were added insequence in to a 4 mL glass vial. The vial was sealed and heated in anisothermal oven at 100° C. and allowed to react solvothermally for 24 h.The product was in the form of cubic shaped pale yellow single crystals.PXRD was checked, it matches the simulated MOF-5 structure (FIG. 4).

¹H NMR of the digested mvMOF-5-AC crystals (400 MHz, DMSO-d6). BDCH₂ δ:8.00 (s, 4H). Br-BDCH₂ δ: 7.78 (d, 1H), 7.94 (d, 1H), 8.10 (s, 1H).Molar ratio based on integration of the peaks: BDC:NH₂-BDC=1:0.61.

mvMOF-5-AD, Zn₄O(BDC)_(1.83)((Cl)₂-BDC)_(1.17):

0.10 mL of (Cl)₂-BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mL ofBDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.20 mL of Zn(NO₃)₂.4H₂Ostock solution (0.30 M, 6.0×10⁻⁵ mol) and 0.60 mL of DEF were added insequence in to a 4 mL glass vial. The vial was sealed and heated in anisothermal oven at 100° C. and allowed to react solvothermally for 24 h.The product was in the form of cubic shaped pale yellow single crystals.PXRD was checked, it matches the simulated MOF-5 structure (FIG. 5).

¹H NMR of the digested mvMOF-5-AD crystals (400 MHz, DMSO-d6). BDCH₂ δ:8.00 (s, 4H). (Cl)₂-BDCH₂ δ: 7.90 (s, 2H). Molar ratio based onintegration of the peaks: BDC:(Cl)₂-BDC=1:0.63.

mvMOF-5-AE, Zn₄O(BDC)_(2.13)(NO₂-BDC)_(0.87):

0.10 mL of NO₂-BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mL ofBDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.20 mL of Zn(NO₃)₂.4H₂Ostock solution (0.30 M, 6.0×10⁻⁵ mol) and 0.60 mL of DEF were added insequence in to a 4 mL glass vial. The vial was sealed and heated in anisothermal oven at 100° C. and allowed to react solvothermally for 48 h.The product was in the form of cubic shaped brown single crystals. PXRDwas checked, it matches the simulated MOF-5 structure (FIG. 6).

¹H NMR of the digested mvMOF-5-AE crystals (400 MHz, DMSO-d6). BDCH₂ δ:8.00 (s, 4H). NO₂-BDCH₂ δ: 7.92 (d, 1H), 8.25 (d, 1H), 8.35 (s, 1H).Molar ratio based on integration of the peaks: BDC:NO₂-BDC=1:0.40.

mvMOF-5-AF, Zn₄O(BDC)_(1.35)((CH₃)₂-BDC)_(1.65):

0.10 mL of (CH₃)₂-BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mLof BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.20 mL of Zn(NO₃)₂.4H₂Ostock solution (0.30 M, 6.0×10⁻⁵ mol) and 0.60 mL of DEF were added insequence in to a 4 mL glass vial. The vial was sealed and heated in anisothermal oven at 100° C. and allowed to react solvothermally for 24 h.The product was in the form of cubic shaped pale yellow single crystals.PXRD was checked, it matches the simulated MOF-5 structure (FIG. 7).

¹H NMR of the digested mvMOF-5-AF crystals (400 MHz, DMSO-d6). BDCH₂ δ:8.00 (s, 4H). (CH₃)₂-BDCH₂ δ: 2.43 (s, 6H), 7.64 (s, 2H). Molar ratiobased on integration of the peaks: BDC:(CH₃)₂-BDC=1:1.24.

mvMOF-5-AG, Zn₄O(BDC)_(1.98)(C₄H₄-BDC)_(1.02):

0.40 mL of C₄H₄-BDCH₂ stock solution (0.025 M, 1.0×10⁻⁵ mol), 0.10 mL ofBDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.20 mL of Zn(NO₃)₂.4H₂Ostock solution (0.30 M, 6.0×10⁻⁵ mol) and 0.30 mL of DEF were added insequence in to a 4 mL glass vial. The vial was sealed and heated in anisothermal oven at 100° C. and allowed to react solvothermally for 24 h.The product was in the form of cubic shaped pale green single crystals.PXRD was checked, it matches the simulated MOF-5 structure (FIG. 8).

¹H NMR of the digested mvMOF-5-AG crystals (400 MHz, DMSO-d6). BDCH₂ δ:8.00 (s, 4H). C₄H₄-BDCH₂ δ: 7.64-7.68 (m, 2H), 8.05 (s, 2H), 8.70-8.74(m, 2H). Molar ratio based on integration of the peaks:BDC:C₄H₄-BDC=1:0.52.

mvMOF-5-AH, Zn₄O(BDC)_(2.04)((C₃H₅O)₂-BDC)_(0.96):

0.10 mL of (C₃H₅O)₂-BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mLof BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.20 mL of Zn(NO₃)₂.4H₂Ostock solution (0.30 M, 6.0×10⁻⁵ mol) and 0.60 mL of DEF were added insequence in to a 4 mL glass vial. The vial was sealed and heated in anisothermal oven at 100° C. and allowed to react solvothermally for 24 h.The product was in the form of cubic shaped brown single crystals. PXRDwas checked, it matches the simulated MOF-5 structure (FIG. 9).

¹H NMR of the digested mvMOF-5-AH crystals (400 MHz, DMSO-d6). BDCH₂ δ:8.00 (s, 4H). (C₃H₅O)₂-BDCH₂ δ: 4.54 (d, 4H), 5.19 (d, 2H), 5.40 (d,2H), 5.94-6.01 (m, 2H), 7.30 (s, 2H).

Molar ratio based on integration of the peaks: BDC:(C₃H₅O)₂-BDC=1:0.46.

mvMOF-5-AI, Zn₄O(BDC)_(2.13)((C₇H₇O)₂-BDC)_(0.87):

0.10 mL of (C₇H₇O)₂-BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mLof BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.20 mL of Zn(NO₃)₂.4H₂Ostock solution (0.30 M, 6.0×10⁻⁵ mol) and 0.60 mL of DEF were added insequence in to a 4 mL glass vial. The vial was sealed and heated in anisothermal oven at 100° C. and allowed to react solvothermally for 24 h.The product was in the form of cubic shaped pale yellow single crystals.PXRD was checked, it matches the simulated MOF-5 structure (FIG. 10).

¹H NMR of the digested mvMOF-5-AI crystals (400 MHz, DMSO-d6). BDCH₂ δ:8.00 (s, 4H). (C₇H₇O)₂-BDCH₂ δ: 5.12 (s, 4H), 7.25-7.44 (m, 12H). Molarratio based on integration of the peaks: BDC:(C₇H₇O)₂-BDC=1:0.40.

mvMOF-5-EI, Zn₄O((C₇H₇O)₂-BDC)_(2.49)(NIDC)_(0.51):

0.10 mL of (C₇H₇O)₂-BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.40 mLof NO₂-BDCH₂ stock solution (0.025 M, 1.0×10⁻⁵ mol), 0.20 mL ofZn(NO₃)₂.4H₂O stock solution (0.30 M, 6.0×10⁻⁵ mol) and 0.30 mL of DEFwere added in sequence in to a 4 mL glass vial. The vial was sealed andheated in an isothermal oven at 100° C. and allowed to reactsolvothermally for 48 h. The product was in the form of cubic shapedbrown single crystals. PXRD was checked, it matches the simulated MOF-5structure (FIG. 11).

¹H NMR of the digested mvMOF-5-EI crystals (400 MHz, DMSO-d6). NO₂-BDCH₂δ: 7.92 (d, 1H), 8.25 (d, 1H), 8.35 (s, 1H). (C₇H₇O)₂-BDCH₂ δ: 5.12 (s,4H), 7.25-7.44 (m, 12H). Molar ratio based on integration of the peaks:NO₂-BDC:(C₇H₇O)₂-BDC=0.20:1.

mvMOF-5-ABC, Zn₄O(BDC)_(1.90)(NH₂-BDC)_(0.11)(Br-BDC)_(0.99):

0.133 mL of BDCH₂ stock solution (0.10 M, 1.33×10⁻⁵ mol), 0.133 mL ofNH₂-BDCH₂ stock solution (0.10 M, 1.33×10⁻⁵ mol), 0.133 mL of Br-BDCH₂stock solution (0.10 M, 1.33×10⁻⁵ mol), 0.40 mL of Zn(NO₃)₂.4H₂O stocksolution (0.30 M, 1.2×10⁻⁴ mol) and 1.20 mL of DEF were added insequence in to a 4 mL glass vial. The vial was sealed and heated in anisothermal oven at 100° C. and allowed to react solvothermally for 48 h.The product was in the form of cubic shaped brown single crystals. PXRDwas checked, it matches the simulated MOF-5 structure (FIG. 12).

¹H NMR of the digested mvMOF-5-ABC crystals (400 MHz, DMSO-d6). BDCH₂ δ:8.00 (s, 4H). NH₂-BDCH₂ δ: 7.03 (d, 1H), 7.40 (d, 1H), 7.38 (s, 1H).Br-BDCH₂ δ: 7.78 (d, 1H), 7.94 (d, 1H), 8.10 (s, 1H). Molar ratio basedon integration of the peaks: BDC:NH₂-BDC:Br-BDC=1:0.052:0.52.

mvMOF-5-AHI, Zn₄O(BDC)_(1.52)((C₃H₅O)₂-BDC)_(0.73)((C₇H₇O)₂-BDC)_(0.75):

0.133 mL of BDCH₂ stock solution (0.10 M, 1.33×10⁻⁵ mol), 0.133 mL of(C₃H₅O)₂-BDCH₂ stock solution (0.10 M, 1.33×10⁻⁵ mol), 0.133 mL of(C₇H₇O)₂-BDCH₂ stock solution (0.10 M, 1.33×10⁻⁵ mol), 0.40 mL ofZn(NO₃)₂.4H₂O stock solution (0.30 M, 1.2×10⁻⁴ mol) and 1.20 mL of DEFwere added in sequence in to a 4 mL glass vial. The vial was sealed andheated in an isothermal oven at 100° C. and allowed to reactsolvothermally for 24 h. The product was in the form of cubic shapedbrown single crystals. PXRD was checked, it matches the simulated MOF-5structure (FIG. 13).

¹H NMR of the digested mvMOF-5-AHI crystals (400 MHz, DMSO-d6). BDCH₂ δ:8.00 (s, 4H). (C₃H₅O)₂-BDCH₂ δ: 4.55 (d, 4H), 5.20 (d, 2H), 5.38 (d,2H), 5.93-6.00 (m, 2H). (C₇H₇O)₂-BDCH₂ δ: 5.12 (s, 4H), 7.26-7.44 (m,12H). Molar ratio based on integration of the peaks:BDC:(C₃H₅O)₂-BDC:(C₇H₇O)₂-BDC=1:0.48:0.50.

mvMOF-5-EHI,Zn₄O(NO₂-BDC)_(1.19)((C₃H₅O)₂-BDC)_(1.07)((C₇H₇O)₂-BDC)_(0.74):

0.133 mL of (C₇H₇O)₂-BDCH₂ stock solution (0.10 M, 1.33×10⁻⁵ mol), 0.133mL of NO₂-BDCH₂ stock solution (0.10 M, 1.33×10⁻⁵ mol), 0.133 mL of(C₃H₅O)₂-BDCH₂ stock solution (0.10 M, 1.33×10⁻⁵ mol), 0.40 mL ofZn(NO₃)₂.4H₂O stock solution (0.30 M, 1.2×10⁻⁴ mol) and 1.20 mL of DEFwere added in sequence in to a 4 mL glass vial. The vial was sealed andheated in an isothermal oven at 100° C. and allowed to reactsolvothermally for 24 h. The product was in the form of cubic shapedbrown single crystals. PXRD was checked, it matches the simulated MOF-5structure (FIG. 14).

¹H NMR of the digested mvMOF-5-EHI crystals (400 MHz, DMSO-d6).NO₂-BDCH₂ δ: 7.93 (d, 1H), 8.25 (d, 1H), 8.35 (s, 1H). (C₃H₅O)₂-BDCH₂ δ:4.55 (d, 4H), 5.20 (d, 2H), 5.38 (d, 2H), 5.93-6.00 (m, 2H).(C₇H₇O)₂-BDCH₂ δ: 5.12 (s, 4H), 7.26-7.44 (m, 12H). Molar ratio based onintegration of the peaks: NO₂-BDC:(C₃H₅O)₂-BDC:(C₇H₇O)₂-BDC=1:0.89:0.62.

mvMOF-5-ABCD,Zn₄O(BDC)_(1.44)(NH₂-BDC)_(0.18)(Br-BDC)_(0.81)((Cl)₂-BDC)_(0.57):

0.10 mL of BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mL ofNH₂-BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mL of Br-BDCH₂stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mL of (Cl)₂-BDCH₂ stocksolution (0.10 M, 1.0×10⁻⁵ mol), 0.40 mL of Zn(NO₃)₂.4H₂O stock solution(0.30 M, 1.2×10⁻⁴ mol) and 1.20 mL of DEF were added in sequence in to a4 mL glass vial. The vial was sealed and heated in an isothermal oven at100° C. and allowed to react solvothermally for 48 h. The product was inthe form of cubic shaped dark brown single crystals. PXRD was checked,it matches the simulated MOF-5 structure (FIG. 15).

¹H NMR of the digested mvMOF-5-ABCD crystals (400 MHz, DMSO-d6). BDCH₂δ: 8.00 (s, 4H). NH₂-BDCH₂ δ: 7.03 (d, 1H), 7.40 (d, 1H), 7.38 (s, 1H).Br-BDCH₂ δ: 7.78 (d, 1H), 7.94 (d, 1H), 8.10 (s, 1H). (Cl)₂-BDCH₂ δ:7.90 (s, 2H). Molar ratio based on integration of the peaks:BDC:NH₂-BDC:Br-BDC:(Cl)₂-BDC=1:0.12:0.56:0.40.

mvMOF-5-ACEF,Zn₄O((BDC)_(1.29)(Br-BDC)_(0.63)(NO₂-BDC)_(0.28)((CH₃)₂-BDC)_(0.80):

0.10 mL of BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mL ofBr-BDCH₂ stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mL of NO₂-BDCH₂stock solution (0.10 M, 1.0×10⁻⁵ mol), 0.10 mL of (CH₃)₂-BDCH₂ stocksolution (0.10 M, 1.0×10⁻⁵ mol), 0.40 mL of Zn(NO₃)₂.4H₂O stock solution(0.30 M, 1.2×10⁻⁴ mol) and 1.20 mL of DEF were added in sequence in to a4 mL glass vial. The vial was sealed and heated in an isothermal oven at100° C. and allowed to react solvothermally for 24 h. The product was inthe form of cubic shaped dark brown single crystals. PXRD was checked,it matches the simulated MOF-5 structure (FIG. 16).

¹H NMR of the digested mvMOF-5-ACEF crystals (400 MHz, DMSO-d6). BDCH₂δ: 8.00 (s, 4H). Br-BDCH₂ δ: 7.78 (d, 1H), 7.94 (d, 1H), 8.10 (s, 1H).NO₂-BDCH₂ δ: 7.92 (d, 1H), 8.25 (d, 1H), 8.35 (s, 1H). (CH₃)₂-BDCH₂ δ:2.43 (s, 6H), 7.64 (s, 2H). Molar ratio based on integration of thepeaks: BDC:Br-BDC:(CH₃)₂-BDC:NO₂-BDC=1:0.49:0.62:0.22.

mvMOF-5-ABCHI,Zn₄O(BDC)_(1.38)(NH₂-BDC)_(0.03)(Br-BDC)_(0.30)((C₃H₅O)₂-BDC)_(0.86)((C₇H₇O)₂-BDC)_(0.43):

80 μL of BDCH₂ stock solution (0.10 M, 8.0×10⁻⁶ mol), 80 μL of NH₂-BDCH₂stock solution (0.10 M, 8.0×10⁻⁶ mol), 80 μL of Br-BDCH₂ stock solution(0.10 M, 8.0×10⁻⁶ mol), 80 μL of (C₃H₅O)₂-BDCH₂ stock solution (0.10 M,8.0×10⁻⁶ mol), 80 μL of (C₇H₇O)₂-BDCH₂ stock solution (0.10 M, 8.0×10⁻⁶mol), 0.40 mL of Zn(NO₃)₂.4H₂O stock solution (0.30 M, 1.2×10⁻⁴ mol) and1.20 mL of DEF were added in sequence in to a 4 mL glass vial. The vialwas sealed and heated in an isothermal oven at 100° C. and allowed toreact solvothermally for 48 h. The product was in the form of cubicshaped dark brown single crystals. PXRD was checked, it matches thesimulated MOF-5 structure (FIG. 17).

¹H NMR of the digested mvMOF-5-ABCHI crystals (400 MHz, DMSO-d6). BDCH₂δ: 8.00 (s, 4H). NH₂-BDCH₂. δ: 7.03 (d, 1H). Br-BDCH₂ δ: 7.78 (d, 1H),7.94 (d, 1H), 8.10 (s, 1H). (C₃H₅O)₂-BDCH₂ δ: 4.54 (d, 4H), 5.19 (d,2H), 5.40 (d, 2H), 5.94-6.01 (m, 2H). (C₇H₇O)₂-BDCH₂ δ: 5.12 (s, 4H),7.25-7.44 (m, 12H). Molar ratio based on integration of the peaks:BDC:NH₂-BDC:Br-BDC:(C₃H₅O)₂-BDC:(C₇H₇O)₂-BDC=1:0.017:0.22:0.62:0.32.

mvMOF-5-ABCGHI,Zn₄O(BDC)_(0.72)(NH₂-BDC)_(0.08)(Br-BDC)_(0.63)(C₄H₄-BDC)_(0.48)((C₃H₅O)₂-BDC)_(0.52)((C₇H₇O)₂-BDC)_(0.57):

67 μL of BDCH₂ stock solution (0.10 M, 6.7×10⁻⁶ mol), 67 μL of NH₂-BDCH₂stock solution (0.10 M, 6.7×10⁻⁶ mol), 67 μL of Br-BDCH₂ stock solution(0.10 M, 6.7×10⁻⁶ mol), 267 μL of C₄H₄-BDCH₂ stock solution (0.10 M,6.7×10⁻⁶ mol), 67 μL of (C₃H₅O)₂-BDCH₂ stock solution (0.10 M, 6.7×10⁻⁶mol), 67 μL of (C₇H₇O)₂-BDCH₂ stock solution (0.10 M, 6.7×10⁻⁶ mol),0.40 mL of Zn(NO₃)₂.4H₂O stock solution (0.30 M, 1.2×10⁻⁴ mol) and 1.0mL of DEF were added in sequence in to a 4 mL glass vial. The vial wassealed and heated in an isothermal oven at 100° C. and allowed to reactsolvothermally for 48 h. The product was in the form of cubic shapeddark brown single crystals. PXRD was checked, it matches the simulatedMOF-5 structure (FIG. 18).

¹H NMR of the digested mvMOF-5-ABCGHI crystals (400 MHz, DMSO-d6). BDCH₂δ: 8.00 (s, 4H). NH₂-BDCH₂ δ: 7.03 (d, 1H). Br-BDCH₂ δ: 7.78 (d, 1H),7.94 (d, 1H), 8.10 (s, 1H). C₄H₄-BDCH₂ δ: 7.64-7.68 (m, 2H), 8.05 (s,2H), 8.70-8.74 (m, 2H). (C₃H₅O)₂-BDCH₂ δ: 4.54 (d, 4H), 5.19 (d, 2H),5.40 (d, 2H), 5.94-6.01 (m, 2H). (C₇H₇O)₂-BDCH₂ δ: 5.12 (s, 4H),7.25-7.44 (m, 12H). Molar ratio based on integration of the peaks:BDC:NH₂-BDC:Br-BDC:C₄H₄-BDC:(C₃H₅O)₂-BDC:(C₇H₇O)₂-BDC=1:0.093:0.87:0.67:0.73:0.80.

mvMOF-5-ABCEGHI, Zn₄O(BDC)_(0.57)(NH₂-BDC)_(0.05)(Br-BDC)_(0.57)(NO₂-BDC)0.39(C₄H₄-BDC)_(0.44)((C₃H₅O)₂-BDC)_(0.42)((C₇H₇O)₂-BDC)_(0.56):

57 μL of BDCH₂ stock solution (0.10 M, 5.7×10⁻⁶ mol), 57 μL of NH₂-BDCH₂stock solution (0.10 M, 5.7×10⁻⁶ mol), 57 μL of Br-BDCH₂ stock solution(0.10 M, 5.7×10⁻⁶ mol), 57 μL of NO₂-BDCH₂ stock solution (0.10 M,5.7×10⁻⁶ mol), 228 μL of C₄H₄-BDCH₂ stock solution (0.10 M, 5.7×10⁻⁶mol), 57 μL of (C₃H₅O)₂-BDCH₂ stock solution (0.10 M, 5.7×10⁻⁶ mol), 57μL of (C₇H₇O)₂-BDCH₂ stock solution (0.10 M, 5.7×10⁻⁶ mol), 0.40 mL ofZn(NO₃)₂.4H₂O stock solution (0.30 M, 1.2×10⁻⁴ mol) and 1.03 mL of DEFwere added in sequence in to a 4 mL glass vial. The vial was sealed andheated in an isothermal oven at 100° C. and allowed to reactsolvothermally for 48 h. The product was in the form of cubic shapeddark brown single crystals. PXRD was checked, it matches the simulatedMOF-5 structure (FIG. 19).

¹H NMR of the digested mvMOF-5-ABCEGHI crystals (400 MHz, DMSO-d6).BDCH₂ δ: 8.00 (s, 4H). NH₂-BDCH₂ δ: 7.03 (d, 1H). Br-BDCH₂ δ: 7.78 (d,1H), 7.94 (d, 1H), 8.10 (s, 1H). NO₂-BDCH₂ δ: 7.92 (d, 1H), 8.25 (d,1H), 8.35 (s, 1H). C₄H₄-BDCH₂ δ: 7.64-7.68 (m, 2H), 8.05 (s, 2H),8.70-8.74 (m, 2H). (C₃H₅O)₂-BDCH₂ δ: 4.54 (d, 4H), 5.19 (d, 2H), 5.40(d, 2H), 5.94-6.01 (m, 2H). (C₇H₇O)₂-BDCH₂ δ: 5.12 (s, 4H), 7.25-7.44(m, 12H). Molar ratio based on integration of the peaks:BDC:NH₂-BDC:Br-BDC:NO₂-BDC:C₄H₄-BDC:(C₃H₅O)₂-BDC:(C₇H₇O)₂-BDC=1:0.077:1:0.69:0.77:0.73:0.96.

mvMOF-5-ABCEFGHI, Zn₄O(BDC)_(0.70)(NH₂-BDC)_(0.011)(Br-BDC)_(0.39)(NO₂-BDC)_(0.21)((CH₃)₂-BDC)_(0.46)(C₄H₄-BDC)_(0.39)((C₃H₅O)₂-BDC)_(0.35)((C₇H₇O)₂-BDC)_(0.39):

50 μL of BDCH₂ stock solution (0.10 M, 5.0×10⁻⁶ mol), 50 μL of NH₂-BDCH₂stock solution (0.10 M, 5.0×10⁻⁶ mol), 50 μL of Br-BDCH₂ stock solution(0.10 M, 5.0×10⁻⁶ mol), 50 μL of NO₂-BDCH₂ stock solution (0.10 M,5.0×10⁻⁶ mol), 50 μL of (CH₃)₂-BDCH₂ stock solution (0.10 M, 5.0×10⁻⁶mol), 200 μL of C₄H₄-BDCH₂ stock solution (0.10 M, 5.0×10⁻⁶ mol), 50 μLof (C₃H₅O)₂-BDCH₂ stock solution (0.10 M, 5.0×10⁻⁶ mol), 50 μL of(C₇H₇O)₂-BDCH₂ stock solution (0.10 M, 5.0×10⁻⁶ mol), 0.40 mL ofZn(NO₃)₂.4H₂O stock solution (0.30 M, 1.2×10⁻⁴ mol) and 1.05 mL of DEFwere added in sequence in to a 4 mL glass vial. The vial was sealed andheated in an isothermal oven at 100° C. and allowed to reactsolvothermally for 48 h. The product was in the form of cubic shapeddark brown single crystals. PXRD was checked, it matches the simulatedMOF-5 structure (FIG. 20).

¹H NMR of the digested mvMOF-5-ABCEFGHI crystals (400 MHz, DMSO-d6).BDCH₂ δ: 8.00 (s, 4H). NH₂-BDCH₂ δ: 7.03 (d, 1H). Br-BDCH₂ δ: 7.78 (d,1H), 7.94 (d, 1H), 8.10 (s, 1H). NO₂-BDCH₂ δ: 7.92 (d, 1H), 8.25 (d,1H), 8.35 (s, 1H). (CH₃)₂-BDCH₂ δ: 2.43 (s, 6H), 7.64 (s, 2H).C₄H₄-BDCH₂ δ: 7.64-7.68 (m, 2H), 8.05 (s, 2H), 8.70-8.74 (m, 2H).(C₃H₅O)₂-BDCH₂ δ: 4.54 (d, 4H), 5.19 (d, 2H), 5.40 (d, 2H), 5.94-6.01(m, 2H). (C₇H₇O)₂-BDCH₂ δ: 5.12 (s, 4H), 7.25-7.44 (m, 12H). Molar ratiobased on integration of the peaks:BDC:NH₂-BDC:Br-BDC:(CH₃)₂-BDC:NO₂-BDC:C₄H₄-BDC:(C₃H₅O)₂-BDC:(C₇H₇O)₂-BDC=1:0.14:0.56:0.29:0.67:0.56:0.48:0.56.

All compounds containing two, three or four different links, andmvMOF-5-ABCEFGHI were scaled up to gram scale with the sameconcentration as described above. PXRD of scaled-up sample are identicalwith the small scale samples. In addition, the bulk homogeneity ofscaled-up sample was checked by solution ¹H NMR of randomly selectedcrystals, and showed identical link ratios in each compound.

Thermalgravimetry.

All samples were run on a TA Instruments Q-500 series thermalgravimetric analyzer with samples held in platinum pans in a continuousair flow atmosphere. Samples were heated at a constant rate of 5° C./minduring all TGA experiments.

Due to the loss of dangling double bond and benzene ring in the links,mvMOFs containing link H and link I will lose weight gradually from 200°C., followed by a steep drop at 400° C. All other mvMOFs will have notlose weight until 400° C.

Solid State ¹³C MAS NMR of Activated mvMOFs.

High resolution solid-state nuclear magnetic resonance (NMR) spectrawere recorded at ambient temperature on a Bruker DSX-300 spectrometerusing a standard Bruker magic angle spinning (MAS) probe with 4 mm(outside diameter) zirconia rotors. Cross-polarization with MAS (CP/MAS)was used to acquire ¹³C data at 75.47 MHz. The ¹H and ¹³C ninety-degreepulse widths were both 4 μs. The CP contact time was varied of 1.5 ms,and 5 ms. High power two-pulse phase modulation (TPPM) 1H decoupling wasapplied during data acquisition. The decoupling frequency correspondedto 72 kHz. The MAS sample spinning rate was 10 kHz. Recycle delays for(CP/MAS) between scans varied between 3 and 20 s, depending upon thecompound as determined by observing no apparent loss in the ¹³C signalintensity from one scan to the next. The ¹³C chemical shifts are givenrelative to tetramethylsilane as zero ppm, calibrated using themethylene carbon signal of adamantane assigned to 37.77 ppm as asecondary reference were listed in Table 2.

Control experiment of ¹³C CP/MAS NMR on link mixture of the same ratioas in mvMOF-5-AB, -ABCD, and -ABCEFGHI was checked, there is asignificant shift of the carbonyl carbon, from 172 to 174 ppm comparingto the experiment on mvMOFs. This demonstrates that all links in thesethree mvMOFs are chemically bonded to zinc cluster. In addition, ¹³Cspectrum of the static sample was acquired using CP/MAS method waschecked to detect mobile guest molecules. In this experiment, recycledelay was set to 20 s to allow enough relaxation between scans. Nodetectable carbon signals were found which confirm the clean porestructure of mvMOFs.

TABLE 2 Summary of ¹³C CP/MAS NMR of selected mvMOF and their linkmixture. Compound Chemical shift δ (ppm) Selected mvMOFs mvMOF-5-AB174.5 149.8 135.5 129. 118. 115.6 mvMOF-5-AC 174.3 135.5 131.3 128. 126.122.3 mvMOF-5-AD 174.4 135.4 133.0 131. 128. mvMOF-5-AE 174.4 151.9135.4 128. 123. mvMOF-5-AF 176.3 174.3 136.9 135. 133. 128.6 18.7mvMOF-5-AG 177.5 147.6 135.5 134. 131. 126.3 125.2 mvMOF-5-AH 175.0153.3 136.3 133. 129. 127.9 119.7 114.2 71.4 mvMOF-5-AI 174.3 152.8135.5 119. 71.5 mvMOF-5-EI 174.3 151.9 145.4 136. 133. 126.8 126.2 118.370.9 mvMOF-5-AHI 174.3 152.3 135.7 132. 127. 118.7 114.5 70.6mvMOF-5-EHI 174.5 152.0 136.6 132. 126. 118.6 115.3 70.5 mvMOF-5-ABCD177.2 175.2 150.3 137. 136. 133.7 132.3 129.4 127.0 123.0 118. 116mvMOF-5-ACEF 177.0 174.9 151.8 136. 135. 133.6 131.4 128.6 126.8 124.0122. 18. mvMOF-5- 177.3 176.4 174.4 152. 137. 135.6 133.9 132.7 131.4126.4 125. 122 119 116 113 71 70 18 Selected Link Mixture Li 172 150135. 129 118. 115. Li 172 150 137. 136 133. 132. 129. 126 123 118. 115.Li 172 152 137. 135 134. 133. 131. 126 125 122. 119. 116. 114 72. 70. 21

Synthesis of Large Single Crystals mvMOF-5-AB-Lsc.

4.20 g Zn(N03)₂.4H₂O (16.0 mmol), 450 mg BDCH₂ (2.7 mmol) and 490 mgNH₂-BDCH₂ (2.7 mmol) were dissolved in 50 mL DEF in a glass beaker bysonicating the mixture for 15 min. The solution was dispensed evenlyinto 10 scintillation vials (20-mL size) by using a plastic syringeequipped with a PTFE filter (Whatman, 0.45 μm pore size). The vials werethen tightly capped and placed in an isothermal oven. The reactions werestopped after being heated at 85° C. for 72 h. The mother liquor in eachvial was decanted while warm and the product was washed with fresh DEF(3×5 mL for each vial). Most of the products were large chunks ofinter-grown cubic brown crystals. Occasionally, some large single cubes(size 1.5-4.0 mm) were observed. In a typical batch as described above,8-13 such crystals could be obtained. The large cubic crystals wereconfirmed to have MOF-5 topology by the coincidence of experimental PXRDpattern with the simulated one and by examination of these crystalsunder an optical microscope (FIGS. 35 A, B and 36). The high initialconcentration is useful to the formation of large mvMOF single crystals.

Synthesis of Large Single Crystal mvMOF-5-ABCD-lsc.

6.20 g Zn(NO₃)₂.4H₂O (23.5 mmol), 332 mg BDCH₂ (2.0 mmol), 362 mgNH₂-BDCH₂ (2.0 mmol), 490 mg Br-BDCH₂ (2.0 mmol), and 470 mg (Cl)₂-BDCH₂(2.0 mmol) were dissolved in 50 mL DEF in a glass beaker by sonicatingthe mixture for 15 min. The solution was dispensed evenly into 10scintillation vials (20-mL size) by using a plastic syringe equippedwith a PTFE filter (Whatman, 0.45 μm pore size). The vials were thentightly capped and placed in an isothermal oven. The reactions werestopped after being heated at 85° C. for 120 h. The mother liquor ineach vial was decanted while warm and the product was washed with freshDEF (3×5 mL for each vial). Most of the products were large chunks ofinter-grown brown cubic crystals. Occasionally, some large single cubes(size 1.0-2.0 mm) were observed. In a typical batch as described above,6-10 such crystals could be obtained. The large cubic crystals wereconfirmed to have MOF-5 topology by the coincidence of experimental PXRDpattern with the simulated one and by examination of these crystalsunder an optical microscope (FIGS. 35 C,D and 37)

Synthesis of Large Single Crystal mvMOF-5-ABCEFGHI-lsc.

4.20 g Zn(NO₃)₂.4H₂O (23.5 mmol), 166 mg BDCH₂ (1.0 mmol), 181 mgNH₂-BDCH₂ (1.0 mmol), 245 mg Br-BDCH₂ (1.0 mmol), 211 mg NO₂-BDCH₂ (1.0mmol), 194 mg (CH₃)₂-BDCH₂ (1.0 mmol), 216 mg C₄H₄-BDCH₂ (1.0 mmol), 278mg (C₃H₅O)₂-BDCH₂ (1.0 mmol), and 374 mg (C₇H₇O)₂-BDCH₂ (1.0 mmol) weredissolved in 50 mL DEF in a glass beaker by sonicating the mixture for15 min. The solution was dispensed evenly into 10 scintillation vials(20-mL size) by using a plastic syringe equipped with a PTFE filter(Whatman, 0.45 μm pore size). The vials were then tightly capped andplaced in an isothermal oven. The reactions were stopped after beingheated at 85° C. for 7 days. The mother liquor in each vial was decantedwhile warm and the product was washed with fresh DEF (3×5 mL for eachvial). Most of the products were large chunks of inter-grown brown cubiccrystals. Occasionally, some large single cubes (size 1.0-2.0 mm) wereobserved. In a typical batch as described above, 5-6 such crystals couldbe obtained. The large cubic crystals were confirmed to have MOF-5topology by the coincidence of experimental PXRD pattern with thesimulated one and by examination of these crystals under an opticalmicroscope (FIGS. 35 E, F and 38).

Solvent-Exchange of MVMOF Large Single Crystals.

The suitable crystals were collected in a 20-mL scintillation vial.After DEF solvent was removed as clean as possible by using a pipette,this open vial was placed in a desiccator saturated with chloroformvapor, which slowly condensed into the vial and accumulated to ˜5 mmtall in 3 days. The crystals were still completely transparent at thispoint. After the removal of the accumulated chloroform, the vial wasfilled with fresh chloroform and capped. The solvent volume was replacedtwice after a 1-day and a 2-day immersion respectively, and was allowedto sit for another 2 days. The total time of chloroform-exchange ofmvMOF large single crystals were 3 days in desiccator and 5 days onbench.

Ratio of the links within mvMOFs were determined by ° H NMR. The resultsare listed in Table 1.

Synthesis of mvMOF-5-AB Series.

0.30M Zn(NO₃)₂.4H₂O stock solution, 0.10M BDCH₂ (link A) and NH₂-BDCH₂(link B) stock solutions were prepared in advance. Various volume oflink A and link B stock solutions were added in to 2.0 mL of 0.30MZn(NO₃)₂.4H₂O stock solution followed by DEF to make the total volume tobe 10 mL in 20 mL glass vials. The vial was sealed and heated in anisothermal oven at 100° C. and allowed to react solvothermally for 48 h.Eleven mvMOF-5-AB compounds were synthesized, a-k respectively, wheremvMOF-5-AB-a only has link A and mvMOF-5-AB-k only has link B, thus theyare actually MOF-5 and IRMOF-3 respectively. All products were in theform of cubic shaped single crystals. The crystallinity of each compoundwas confirmed by PXRD, the very high degree of correspondence with thesimulated MOF-5 pattern indicates that these compounds inherent theunaltered MOF-5 topology (FIG. 40). Ratio of the links within mvMOFs aredetermined by ¹H NMR in the same way described previously. Table 3summarized the amount of stock solutions were used in each compound andtheir initial link ratios and those of their products. The percent ratioof B in crystal product of mvMOF-5-AB series was plotted against theirinitial stoichiometric ratio (FIG. 40). More link B was found in thecrystal product as more link B was added as starting materials. Thisclearly demonstrates that the link ratio in mvMOFs can be fine-tuned inwhole range simply by controlling the initial amount of links usedduring synthesis. Since NH₂-BDC (link B) has its characteristic redcolor in the MOF structure, here a gradual change in the color ofas-synthesized mvMOF-5-AB crystals was observed, which further indicatesthe capability of precise control of link ratio in mvMOFs. As thepercentage of link B increases from compound -a to -k, the color of thecrystal change form colorless to red and then dark red (FIG. 40).

TABLE 3 Summary of synthesis of mvMOF-5-AB series, their addedstoichiometric link ratio and the ratio found in their crystals. Link ALink B B:A B:A Ratio Solution/ Solution/ Zn(NO₃)₂•4H₂O/ stoichiometricin crystal Compound mL mL mL Ratio product mvMOF-5-AB-a 2.0 0 2.0  0:10  0:10 mvMOF-5-AB-b 1.8 0.2 2.0 1:9 0.01:1  mvMOF-5-AB-c 1.7 0.3 2.0 1:60.9:1 mvMOF-5-AB-d 1.5 0.5 2.0 1:3 0.15:1  mvMOF-5-AB-e 1.3 0.7 2.0 1:20.26:1  mvMOF-5-AB-f 1.0 1.0 2.0 1:1 0.43:1  mvMOF-5-AB-g 0.7 1.3 2.02:1 1.2:1 mvMOF-5-AB-h 0.5 1.5 2.0 3:1 1.5:1 mvMOF-5-AB-i 0.3 1.7 2.06:1 3.4:1 mvMOF-5-AB-j 0.2 1.8 2.0 9:1 5.1:1 mvMOF-5-AB-k 0 2.0 2.010:0   10:0 mvMOF-5-AB-a and mvMOF-5-AB-k are actually MOF-5 and IRMOF-3respectively.

Synthesis of mvMOF-5-AI Series.

0.30M Zn(NO₃)₂.4H₂O stock solution, 0.10M BDCH₂ (link A) and(C₇H₇O)₂-BDCH₂ (link I) stock solutions were prepared in advance.Various volume of link A and link I stock solutions were added in to 2.0mL of 0.30M Zn(NO₃)₂.4H₂O stock solution followed by DEF to make thetotal volume to be 10 mL in 20 mL glass vials. The vial was sealed andheated in an isothermal oven at 100° C. and allowed to reactsolvothermally for 24 h. Three mvMOF-5-AI compounds were synthesized,a-c respectively. All products were in the form of cubic shaped singlecrystals. The crystallinity of each compound was confirmed by PXRD, thevery high degree of correspondence with the simulated MOF-5 patternindicates that these compounds inherent the unaltered MOF-5 topology(FIG. 42). Ratio of the links within mvMOFs are determined by ¹H NMR inthe same way described previously. Table 4 summarized the amount ofstock solutions were used in each compound and their initial link ratiosand those of their products. Similar to mvMOF-5-AB series, percent ratioof I in crystal product of mvMOF-5-AI series increases as more link Iwas used in starting material.

TABLE 4 Summary of synthesis of mvMOF-5-AI series, their addedstoichiometric link ratio and the ratio found in their crystals. Link ALink B I:A I:A Solu- Solu- stoichio- Ratio in tion/ tion/ Zn(NO₃)₂•4H₂O/metric crystal Compound mL mL mL Ratio product mvMOF-5-AI-a 1.0 1.0 2.01:1 0.43:1   mvMOF-5-AI-b 1.3 0.7 2.0 2:1 0.98:1   mvMOF-5-AI-c 1.5 0.52.0 3:1 1.9:1  

Synthesis of mvMOF-5-ABCD Series.

0.30M Zn(NO₃)₂.4H₂O stock solution, 0.10M BDCH₂ (link A) and NH₂-BDCH₂(link B), Br-BDCH₂ (link C), (Cl)₂-BDCH₂ (link D) stock solutions wereprepared in advance. Various volume of link A and link I stock solutionswere added in to 2.0 mL of 0.30M Zn(NO₃)₂.4H₂O stock solution followedby adding DEF to make the total volume to be 10 mL in 20 mL glass vials.The vial was sealed and heated in an isothermal oven at 100° C. andallowed to react solvothermally for 48 h. Five mvMOF-5-ABCD compoundswere synthesized, a-e respectively. All products were in the form ofcubic shaped single crystals. The crystallinity of each compound wasconfirmed by PXRD, the very high degree of correspondence with thesimulated MOF-5 pattern indicates that these compounds inherent theunaltered MOF-5 topology (FIG. 43). Ratio of the links within mvMOFs aredetermined by ¹H NMR in the same way described in section 1. Table 5summarized the amount of stock solutions were used in each compound andin Table 1 (Control of Link Ratio part) in the text. When comparing thelink ratios of mvMOF-5-ABCD crystals to the stoichiometric ratio oflinks used in the synthesis of each compound, as increase (or decrease)in the amount of certain links used as in starting materials, the ratioin the resulting mvMOF increases (or decreases) correspondently. Theseagain demonstrate that the ratio of link within mvMOFs is controllable.

TABLE 5 Summary of synthesis of mvMOF-5-ABCD series. Link Link Link LinkA B C D Solu- Solu- Solu- Solu- tion/ tion/ tion/ tion/ Zn(NO₃)₂•4H₂O/Compound mL mL mL mL mL mvMOF-5-ABCD-a 0.50 0.50 0.50 0.50 2.0mvMOF-5-ABCD-b 0.25 0.50 0.50 0.75 2.0 mvMOF-5-ABCD-c 0.75 0.50 0.500.25 2.0 mvMOF-5-ABCD-d 0.50 0.75 0.25 0.50 2.0 mvMOF-5-ABCD-e 0.50 0.250.75 0.50 2.0

Single X-Ray Diffraction Data Collection, Structure Solution, andRefinement Procedures for mvMOF-5-AC and -ACEF.

General procedures for single crystal data collection, structuresolution, and refinement are presented here. Unique details for eachstructure including structural disorders are described prior to theexperimental and metrical listings for each structure.

General Data Collection and Refinement Procedures:

Data were collected on a Bruker SMART APEXII three circle diffractometerequipped with a CCD area detector and operated at 1200 W power (40 kV,30 mA) to generate Cu Kα radiation (λ=1.5418 Å). The incident X-ray beamwas focused and monochromated using Bruker Excalibur Gobel mirroroptics. Crystals were all mounted in flame sealed borosilicatecapillaries containing a small amount of mother liquor to preventdesolvation during data collection.

Initial ω-φ scans of each specimen were taken to obtain preliminary unitcell parameters and to assess the mosaicity (i.e. breadth of spotsbetween frames) of the crystal to select the required frame width fordata collection. For all cases frame widths of 0.5° were judged to beappropriate and full hemispheres of data were collected using the BrukerAPEX2 software suite to carry out overlapping φ and ω scans at differentdetector (2θ) settings. Following data collection, reflections weresampled from all regions of the Ewald sphere to redetermine unit cellparameters for data integration and to check for rotational twinningusing CELL_NOW.

Following exhaustive review of collected frames the resolution of thedataset was judged, and, if necessary, regions of the frames where nocoherent scattering was observed were removed from consideration fordata integration. Data were integrated using Bruker APEX2 V 2.1 softwarewith a narrow frame algorithm and a 0.400 fractional lower limit ofaverage intensity. Absorption corrections were ineffectual for improvingthe quality of the data, which is not unexpected for small crystals oflow density materials containing primarily light atoms.

The space group determination and tests for merohedral twinning werecarried out using XPREP. In all cases the highest possible space groupwas chosen and no indications of merohedral twinning were observed. Allstructures were solved by direct methods and refined using theSHELXTL'97 software suite. Atoms were located from iterative examinationof difference F-maps following least-squares refinements of the earliermodels. Final models were refined anisotropically (if the number of datapermitted and stable refinement could be reached) until full convergencewas achieved. Partial occupancies were assigned to each pair of atoms inthe disordered groups. Some atoms could not be located precisely due tohigh disorder and low occupancy (Nitro group on link E in mvMOF-ACEF).Hydrogen atoms were placed in calculated positions and included asriding atoms. Modeling of electron density within the voids of theframeworks did not lead to identification of all guest entities instructures due to the lowered resolution of the data. This difficulty,which is typical of porous crystals that contain solvent filled pores,lies in the raw data where observed strong (high intensity) scatteringbecomes limited to ˜1.0 Å at best, with higher resolution data presentbut weak (low intensity). As is a common strategy for improving X-raydata, increasing the exposure time of the crystal to X-rays did notameliorate the quality of the high angle data in these cases, as theintensity from low angle data saturated the detector and minimalimprovement in the high angle data was achieved. Additionally, diffusescattering from the disordered functional groups on the phenyl unit ofthe MOF backbone and solvents in the void spaces within the crystal andsolvents from the capillary used to mount the crystal contributed to thebackground noise and sometimes to the ‘washing out’ of high angle data.For these extended framework structures it was also more reasonable tomodel against data collected at a higher range of temperatures (−50 to−15° C., rather than −120 to −100° C.) when guest entities in thestructures were allowed to move freely and therefore did not contributecoherent scattering terms to the observed structure factors.

To prove the correctness of the atomic positions in the framework, theapplication of the SQUEEZE routine of A. Spek has been performed whenapplicable. However, atomic co-ordinates for the “non-SQUEEZE”structures have also been presented and the CIFs were also submitted forthe cases where the program SQUEEZE has been employed. All structureswere examined using the Adsym subroutine of PLATON to assure that noadditional symmetry could be applied to the models. All ellipsoids inORTEP diagrams are displayed at the 15% probability level unless notedotherwise. For all structures the elevated R-values are commonlyencountered in MOF crystallography, for the reasons expressed above.

Experimental and Refinement Details for mvMOF-5-AC.

A colorless parallelepiped crystal (0.41×0.41×0.28 mm³) of mvMOF-5-ACwas placed in a 0.5 mm diameter borosilicate capillary along with asmall amount of mother liquor. The capillary was flame sealed andmounted on a SMART APEXII three circle diffractometer equipped with aCCD area detector and operated at 1200 W power (40 kV, 30 mA) togenerate Cu Kα radiation (λ=1.5418 Å) while being cooled to 258(2) K ina liquid N₂ cooled stream of nitrogen. Full hemispheres of data werecollected, using the Bruker APEX2 software suite to carry outoverlapping φ and ω scans at three different detector (2θ) settings(2θ=28, 60, 1000). A total of 14178 reflections were collected of which2951 were unique and 1994 of these were greater than 2σ(I). The range ofθ was from 2.97 to 41.28°. Analysis of the data showed negligible decayduring collection. The program Scale was performed to minimizedifferences between symmetry related or repeatedly measured reflections.

The structure was solved in the monoclinic C2/m space group with Z=8using direct methods. Zn and O atoms in the backbone of the frameworkwere refined anisotropically and all other nonhydrogen atoms wererefined isotropicly, with hydrogen atoms generated as spheres riding thecoordinates of their parent atoms. The attempts made to model solventmolecules did not lead to identification of guest entities. Since thesolvent is not bonded to the framework, imprecise locations for solventmolecules were expected for the MOF structure. In addition, very highdisplacement parameters, high esd's and partial occupancy due to thedisorder made it impossible to determine accurate positions for thesolvent molecules. Nonetheless, assignment and refinement of thebackbone framework and —Br group of mvMOF-5-AC was unambiguous, asjudged by the resulting bond and angle metrics.

To improve the atomic positions in the framework the application of theSQUEEZE routine of A. Spek has been performed. However, atomicco-ordinates for the “non-SQUEEZE” structure are also presented. Finalfull matrix least-squares refinement on F² converged to R1=0.1257(F>2σ(F)) and wR2=0.3084 (all data) with GOF=0.998. For the structurewhere the SQUEEZE program has not been employed, final full matrixleast-squares refinement on F² converged to R1=0.1892 (F>2σ(F)) andwR2=0.4184 (all data) with GOF=1.426. When only framework atoms wereincluded in the latter structure factor calculation, the residualelectron density in the F-map was located within the pores ofmvMOF-5-AC. The empirical formula for crystal structure refinement isC12 H5.43 Br0.57 O7.25 Zn2, with a density of 0.683 g cm⁻³, based on themeasured ratio of the two types of links in the crystal by ¹H NMR.

TABLE 6 Crystal data and structure refinement for mvMOF-5-AC. Empiricalformula C12 H5.43 Br0.57 O7.25 Zn2 Formula weight   441.88 Temperature258(2) K. Wavelength 1.54178 Å Crystal system Monoclinic Space groupC2/m Unit cell dimensions a = 31.6131(7) Å α = 90°. b = 18.252 Å β =125.26°. c = 18.252 Å γ = 90°. Volume 8598.74(19) Å³ Z    8 Density(calculated) 0.683 g/cm³ Absorption coefficient 2.102 mm⁻¹ F(000)  1723Crystal size 0.28 × 0.41 × 0.41 mm³ Theta range for data collection 2.97to 41.28°. Index ranges −27 <= h <= 26, −15 <= k <= 15, −15 <= l <= 15Reflections collected 14178 Independent reflections 2951 [R(int) =0.3363] Completeness to theta = 41.28° 99.5% Refinement methodFull-matrix least-squares on F² Data/restraints/parameters 2951/0/154Goodness-of-fit on F²   1.426 Final R indices [I > 2sigma(I)] R_(I) =0.1711, wR₂ = 0.4040 R indices (all data) R_(I) = 0.1892, wR₂ = 0.4184Largest diff. peak and hole 1.266 and −0.739 e.Å⁻³

TABLE 7 Crystal data and structure refinement for mvMOF-5-AC (SQUEEZE).Empirical formula C12 H5.43 Br0.57 O7.25 Zn2 Formula weight  441.88Temperature 258(2) K. Wavelength 1.54178 Å Crystal system MonoclinicSpace group C2/m Unit cell dimensions a = 31.6131(7) Å α = 90°. b =18.252 Å β = 125.26°. c = 18.252 Å γ = 90°. Volume 8598.74(19) Å³ Z   8Density (calculated) 0.683 g/cm³ Absorption coefficient 2.102 mm⁻¹F(000)  1723 Crystal size 0.41 × 0.41 × 0.28 mm³ Theta range for datacollection 2.97 to 41.28°. Index ranges −27 <= h <= 26, −15 <= k <= 15,−15 <= l <= 15 Reflections collected 14178 Independent reflections 2951[R(int) = 0.3267] Completeness to theta = 41.28° 99.5% Refinement methodFull-matrix least-squares on F² Data/restraints/parameters 2951/0/144Goodness-of-fit on F²   0.998 Final R indices [I > 2sigma(I)] R_(I) =0.1102, wR₂ = 0.2855 R indices (all data) R_(I) = 0.1257, wR₂ = 0.3084Largest diff. peak and hole 0.983 and −0.426 e.Å⁻³

TABLE 8 Atomic coordinates (×10⁴) and equivalent isotropic displacementparameters (Å² × 10³) for mvMOF-5-AC. U(eq) is defined as one third ofthe trace of the orthogonalized U^(ij) tensor. x y z U (eq) Zn (1) 2937(1) 0 3808 (2) 74 (2) Zn (2) 2936 (1) 0 2061 (2) 73 (2) Zn (3) 2063 (1)872 (1) 2063 (2) 73 (1) O (1) 2501 (6) 0 2502 (9) 57 (4) O (2) 3667 (7)0 4289 (13) 107 (6) O (3) 3683 (7) 0 3084 (17) 119 (7) C (1) 3899 (15) 03930 (30) 108 (11) C (2) 4460 (12) 0 4460 (20) 95 (9) C (3) 4726 (14) 04090 (30) 129 (12) Br (3) 4470 (20) 0 2760 (40) 193 C (4) 4750 (15) 05380 (30) 141 (13) Br (4) 4450 (30) 0 6130 (50) 211 O (4) 2816 (6) 865(8) 4299 (10) 116 (5) O (5) 2173 (6) 1484 (8) 3037 (11) 116 (5) C (10)2488 (10) 1394 (14) 3864 (19) 101 (7) C (11) 2497 (8) 1973 (12) 4468(15) 99 (6) C (12) 2179 (11) 2552 (17) 4100 (20) 149 (10) Br (12) 18042722 2874 224 C (13) 2825 (12) 1924 (18) 5360 (20) 166 (11) Br (13) 32931135 5838 249 O (6) 2823 (7) 861 (8) 1351 (10) 115 (5) O (7) 2183 (6)1479 (8) 1323 (10) 118 (5) C (20) 2492 (10) 1386 (15) 1098 (16) 103 (7)C (21) 2493 (9) 1944 (13) 529 (15) 109 (7) C (22) 2177 (10) 2538 (15)277 (17) 141 (9) Br (22) 1631 2486 385 212 C (23) 2817 (10) 1902 (16)243 (18) 147 (10) Br (23) 3186 1057 450 221 O (8) 1338 (5) 627 (8) 1346(10) 114 (5) C (30) 1135 (13) 0 1150 (20) 101 (10) C (31) 533 (12) 0 530(20) 104 (9) C (32) 271 (9) 637 (16) 275 (17) 146 (10) Br (32) 655 1523680 220

TABLE 9 Bond lengths [Å] and angles [°] for mvMOF-5-AC. Zn(1)-O(2) 1.938(19) C(10)-C(11) 1.52 (3) Zn(1)-O(1) 1.946 (14) C(11)-C(13) 1.34 (3)Zn(1)-O(4) 1.958 (13) C(11)-C(12) 1.34 (3) Zn(1)-O(4)#1 1.958 (13)C(12)-C(13)#3 1.38 (3) Zn(2)-O(6)#1 1.934 (14) C(12)-H(12) 0.9300Zn(2)-O(6) 1.934 (14) C(13)-C(12)#3 1.38 (3) Zn(2)-O(1) 1.952 (14)C(13)-H(13) 0.9300 Zn(2)-O(3) 1.99 (2) O(6)-C(20) 1.29 (3) Zn(3)-O(8)1.923 (14) O(7)-C(20) 1.27 (3) Zn(3)-O(7) 1.946 (14) C(20)-C(21) 1.45(3) Zn(3)-O(1) 1.952 (9) C(21)-C(22) 1.36 (3) Zn(3)-O(5) 1.954 (13)C(21)-C(23) 1.40 (3) O(1)-Zn(3)#1 1.952 (9) C(22)-C(23)#4 1.40 (3)O(2)-C(1) 1.23 (4) C(22)-H(22) 0.9300 O(3)-C(1) 1.28 (4) C(23)-C(22)#41.40 (3) C(1)-C(2) 1.45 (4) C(23)-H(23) 0.9300 C(2)-C(3) 1.35 (4)O(8)-C(30) 1.258 (18) C(2)-C(4) 1.38 (4) C(30)-O(8)#1 1.258 (18)C(3)-C(4)#2 1.35 (4) C(30)-C(31) 1.55 (4) C(3)-H(3) 0.9300 C(31)-C(32)#11.35 (3) C(4)-C(3)#2 1.35 (4) C(31)-C(32) 1.35 (3) C(4)-H(4) 0.9300C(32)-C(32)#5 1.40 (5) O(4)-C(10) 1.30 (3) C(32)-H(32) 0.9300 O(5)-C(10)1.25 (3) O(2)-Zn(1)-O(1) 111.8 (8) C(2)-C(3)-C(4)#2 120 (4)O(2)-Zn(1)-O(4) 106.7 (6) C(2)-C(3)-H(3) 119.8 O(1)-Zn(1)-O(4) 111.9 (5)C(4)#2-C(3)-H(3) 119.8 O(2)-Zn(1)-O(4)#1 106.7 (6) C(3)#2-C(4)-C(2) 123(4) O(1)-Zn(1)-O(4)#1 111.9 (5) C(3)#2-C(4)-H(4) 118.4 O(4)-Zn(1)-O(4)#1107.5 (9) C(2)-C(4)-H(4) 118.4 O(6)#1-Zn(2)-O(6) 108.6 (9)C(10)-O(4)-Zn(1) 128.1 (16) O(6)#1-Zn(2)-O(1) 112.0 (5) C(10)-O(5)-Zn(3)128.5 (16) O(6)-Zn(2)-O(1) 112.0 (5) O(5)-C(10)-O(4) 129 (2)O(6)#1-Zn(2)-O(3) 106.7 (6) O(5)-C(10)-C(11) 117 (2) O(6)-Zn(2)-O(3)106.7 (6) O(4)-C(10)-C(11) 114 (2) O(1)-Zn(2)-O(3) 110.5 (8)C(13)-C(11)-C(12) 120 (2) O(8)-Zn(3)-O(7) 107.0 (7) C(13)-C(11)-C(10)121 (3) O(8)-Zn(3)-O(1) 111.9 (5) C(12)-C(11)-C(10) 119 (2)O(7)-Zn(3)-O(1) 111.9 (6) C(11)-C(12)- 120 (3) O(8)-Zn(3)-O(5) 105.6 (7)C(11)-C(12)-H(12) 120.0 O(7)-Zn(3)-O(5) 107.6 (7) C(13)#3-C(12)- 120.0O(1)-Zn(3)-O(5) 112.4 (6) C(11)-C(13)- 120 (3) Zn(1)-O(1)-Zn(3)#1 109.6(5) C(11)-C(13)-H(13) 119.9 Zn(1)-O(1)-Zn(3) 109.6 (5) C(12)#3-C(13)-119.9 Zn(3)#1-O(1)-Zn(3) 109.2 (7) C(20)-O(6)-Zn(2) 129.9 (16)Zn(1)-O(1)-Zn(2) 109.6 (7) C(20)-O(7)-Zn(3) 130.0 (17)Zn(3)#1-O(1)-Zn(2) 109.4 (5) O(7)-C(20)-O(6) 127 (2) Zn(3)-O(1)-Zn(2)109.4 (5) O(7)-C(20)-C(21) 117 (2) C(1)-O(2)-Zn(1) 133 (2)O(6)-C(20)-C(21) 116 (2) C(1)-O(3)-Zn(2) 130 (2) C(22)-C(21)-C(23) 118(2) O(2)-C(1)-O(3) 125 (4) C(22)-C(21)-C(20) 120 (2) O(2)-C(1)-C(2) 122(4) C(23)-C(21)-C(20) 122 (2) O(3)-C(1)-C(2) 113 (4) C(21)-C(22)- 121(2) C(3)-C(2)-C(4) 116 (3) C(21)-C(22)-H(22) 119.5 C(3)-C(2)-C(1) 123(3) C(23)#4-C(22)- 119.5 C(4)-C(2)-C(1) 120 (3) C(21)-C(23)- 121 (3)C(21)-C(23)-H(23) 119.6 C(32)#1-C(31)- 120 (3) C(22)#4-C(23)-H(23) 119.6C(32)#1-C(31)- 120.2 (16) C(30)-O(8)-Zn(3) 128.1 (19) C(32)-C(31)-C(30)120.2 (16) O(8)-C(30)-O(8)#1 131 (3) C(31)-C(32)- 120.2 (16)O(8)-C(30)-C(31) 114.6 (16) C(31)-C(32)-H(32) 119.9 O(8)#1-C(30)-C(31)114.6 (16) C(32)#5-C(32)- 119.9Symmetry Transformations Used to Generate Equivalent Atoms:

  #1 x, −y, z #2 −x + 1, −y, −z + 1 #3 −x + ½, −y + ½, −z + 1 #4 −x + ½,−y + ½,−z #5 −x, y, −z

TABLE 10 Anisotropic displacement parameters (Å² × 10³) for mvMOF-5-AC.U¹¹ U²² U³³ U²³ U¹³ U¹² Zn(1) 86 (3) 75 (2) 64 (3) 0 46 (2) 0 Zn(2) 85(3) 76 (2) 67 (2) 0 50 (2) 0 Zn(3) 84 (2) 69 (2) 71 (2) 3 (1) 47 (2) 4(1) O(1) 70 (10) 66 (10) 40 (9) 0 35 (8) 0 O(2) 67 (12) 148 (18) 93 (14)0 38 (11) 0 O(3) 81 (14) 141 (18) 140 (20) 0 69 (14) 0 O(4) 153 (13) 107(12) 97 (11) −36 (9) 78 (10) 3 (11) O(5) 153 (13) 95 (10) 106 (12) −29(8) 78 (11) 18 (9) O(6) 156 (14) 111 (12) 122 (12) 33 (9) 106 (11) 3(11) O(7) 158 (14) 92 (10) 127 (12) 39 (9) 96 (11) 5 (9) O(8) 86 (10)117 (12) 130 (12) 7 (10) 57 (9) 23 (9) The anisotropic displacementfactor exponent takes the form: −2π²[h² a*²U¹¹ + . . . + 2 h k a* b*U¹²]

TABLE 11 Hydrogen coordinates (×10⁴) and isotropic displacementparameters ( Å² × 10³) for mvMOF-5-AC. x y z U(eq) H(3) 4549 0 3470 155H(4) 4576 0 5655 169 H(12) 1962 2600 3477 179 H(13) 3058 1535 5616 199H(22) 1954 2572 452 170 H(23) 3033 1498 399 176 H(32) 450 1079 470 176

Experimental and Refinement Details for mvMOF-5-ACEF.

A red parallelepiped crystal (0.30×0.30×0.21 mm³) of mvMOF-5-ACEF wasplaced in a 0.4 mm diameter borosilicate capillary along with a smallamount of mother liquor. The capillary was flame sealed and mounted on aSMART APEXII three circle diffractometer equipped with a CCD areadetector and operated at 1200 W power (40 kV, 30 mA) to generate Cu Kαradiation (λ=1.5418 Å) while being cooled to 233(2) K in a liquid N2cooled stream of nitrogen. Full hemispheres of data were collected usingthe Bruker APEX2 software suite to carry out overlapping φ and ω scansat three different detector (2θ) settings (2θ=28, 60, 1000). A total of13758 reflections were collected of which 2855 were unique and 1918 ofthese were greater than 2σ(I). The range of θ was from 2.99 to 41.02°.Analysis of the data showed negligible decay during collection. Theprogram Scale was performed to minimize differences between symmetryrelated or repeatedly measured reflections.

The structure was solved in the monoclinic C2/m space group with Z=8using direct methods. Zn atoms in the backbone of the framework wererefined anisotropically and all other nonhydrogen atoms were refinedisotropicly, with hydrogen atoms generated as spheres riding thecoordinates of their parent atoms. The attempts made to model solventmolecules did not lead to identification of guest entities. Since thesolvent is not bonded to the framework, imprecise locations of solventmolecules were expected for the MOF structure. In addition, very highdisplacement parameters, high esd's and partial occupancy due to thedisorder made it impossible to determine accurate positions for thesolvent molecules. Nonetheless, assignment and refinement of thebackbone framework and the general location of the functional group (—Brand —CH₃) of mvMOF-5-ACEF was unambiguous, as judged by the resultingbond and angle metrics. Given the low occupancy (only 9.4% in molarpercent) and its disorder over four positions, the constitution of NO₂,present in a very minor amount, thus has been neglected in thisrefinement.

To improve the correctness of the atomic positions in the framework theapplication of the SQUEEZE routine of A. Spek has been performed.However atomic co-ordinates for the “non-SQUEEZE” structure are alsopresented. Final full matrix least-squares refinement on F² converged toR1=0.1219 (F>2σ(F)) and wR2=0.3041 (all data) with GOF=1.003. For thestructure where the SQUEEZE program has not been employed, final fullmatrix least-squares refinement on F² converged to R1=0.1737 (F>2σ(F))and wR2=0.3972 (all data) with GOF=1.378. When only framework atoms wereincluded in the latter structure factor calculation, the residualelectron density in the F-map was located within the pores ofmvMOF-5-ACEF. The empirical formula for crystal structure refinement isC12.81 H6.65 Br0.31 N0.14 O7.78 Zn2, based on the measured ratio of thefour types of links in the crystal by ¹H NMR.

TABLE 12 Crystal data and structure refinement for mvMOF-5-ACEF.Empirical formula C12.81 H6.65 Br0.31 N0.14 O7.78 Zn2 Formula weight  443.02 Temperature 233(2) K. Wavelength 1.54178 Å Crystal systemMonoclinic Space group C2/m Unit cell dimensions a = 31.3518(7) Å α =90°. b = 18.101 Å β = 125.26°. c = 18.101 Å γ = 90°. Volume 8387.24(19)Å³ Z    8 Density (calculated) 0.702 g/cm³ Absorption coefficient 1.893mm⁻¹ F(000)  1743 Crystal size 0.30 × 0.30 × 0.21 mm³ Theta range fordata collection 2.99 to 41.02°. Index ranges −26 <= h <= 25, −15 <= k <=15, −15 <= l <= 15 Reflections collected 13758 Independent reflections2855 [R(int) = 0.2887] Completeness to theta = 41.02° 99.2% Refinementmethod Full-matrix least-squares on F² Data/restraints/parameters2855/0/116 Goodness-of-fit on F²   1.378 Final R indices [I > 2sigma(I)]R_(I) = 0.1572, wR₂ = 0.3799 R indices (all data) R_(I) = 0.1737, wR₂ =0.3972 Largest diff. peak and hole 1.366 and −0.522 e.Å⁻³

TABLE 13 Crystal data and structure refinement for mvMOF-5-ACEF(SQUEEZE). Empirical formula C12.81 H6.65 Br0.31 N0.14 O7.78 Zn2 Formulaweight  443.02 Temperature 233(2) K. Wavelength 1.54178 Å Crystal systemMonoclinic Space group C2/m Unit cell dimensions a = 31.3518(7) Å α =90°. b = 18.101 Å β = 125.26°. c = 18.101 Å γ = 90°. Volume 8387.24(19)Å³ Z   8 Density (calculated) 0.702 g/cm³ Absorption coefficient 1.893mm⁻¹ F(000)  1743 Crystal size 0.30 × 0.30 × 0.21 mm³ Theta range fordata collection 2.99 to 41.02°. Index ranges −26 <= h <= 25, −15 <= k <=15, −15 <= l <= 15 Reflections collected 13758 Independent reflections2855 [R(int) = 0.2767] Completeness to theta = 41.02° 99.2% Refinementmethod Full-matrix least-squares on F² Data/restraints/parameters2855/0/116 Goodness-of-fit on F²   1.003 Final R indices [I > 2sigma(I)]R_(I) = 0.1057, wR₂ = 0.2771 R indices (all data) R_(I) = 0.1219, wR₂ =0.3041 Largest diff. peak and hole 0.833 and −0.636 e.Å⁻³

TABLE 14 Atomic coordinates (×10⁴) and equivalent isotropic displacementparameters (Å² × 10³) for mvMOF-5-ACEF. U(eq) is defined as one third ofthe trace of the orthogonalized U^(ij) tensor. x y z U (eq) Zn (1) 2062(1) 5000 1187 (2) 107 (2) Zn (2) 2936 (1) 4127 (1) 2937 (1) 107 (1) Zn(3) 2065 (1) 5000 2938 (2) 107 (2) O (1) 2511 (5) 5000 2514 (9) 93 (4) O(2) 1356 (7) 5000 698 (13) 156 (6) O (3) 1356 (7) 5000 1997 (13) 159 (6)O (4) 2178 (5) 4187 (7) 718 (9) 161 (5) O (5) 2822 (5) 3529 (7) 1999 (9)160 (5) O (6) 2169 (5) 4181 (8) 3638 (9) 170 (5) O (7) 2825 (5) 3528 (8)3644 (9) 164 (5) O (8) 3645 (5) 4347 (8) 3658 (9) 161 (4) C (1) 1161(13) 5000 1120 (20) 171 (11) C (2) 493 (12) 5000 510 (20) 162 (10) C (3)251 (15) 5000 −440 (30) 189 (13) Br (3) 609 5000 −1045 283 C (3M) 5345000 −916 283 C (4) 239 (14) 5000 930 (20) 180 (12) Br (4) 614 5000 2250270 C (4M) 544 5000 1973 270 C (5) 2484 (8) 3673 (12) 1129 (15) 157 (7)C (6) 2518 (8) 3001 (12) 539 (15) 152 (7) C (7) 2169 (9) 3099 (15) −449(18) 188 (9) Br (7) 1703 3924 −1067 283 C (7M) 1801 3749 −935 283 C (8)2856 (9) 2411 (14) 968 (17) 186 (9) Br (8) 3364 2322 2332 278 C (8M)3258 2344 2045 278 C (9) 2503 (9) 3672 (12) 3838 (14) 161 (8) C (10)2495 (8) 3012 (12) 4483 (14) 158 (7) C (11) 2852 (10) 2402 (15) 4738(17) 197 (10) Br (11) 3352 2289 4364 295 C (11M) 3247 2315 4442 295 C(12) 2137 (10) 3113 (15) 4739 (17) 202 (10) Br (12) 1640 3971 4352 303 C(12M) 1746 3790 4432 303 C (13) 3848 (11) 5000 3840 (20) 157 (10) C (14)4505 (13) 5000 4510 (20) 169 (11) C (15) 4754 (6) 4293 (11) 4737 (14)168 (8) Br (15) 4399 3354 4342 252 C (15M) 4473 3557 4423 252

TABLE 15 Bond lengths [Å] and angles [°] for mvMOF-5-ACEF. Zn(1)-O(4)#11.838 (14) C(3)-C(4)#2 1.25 (4) Zn(1)-O(4) 1.838 (14) C(3)-H(3) 0.9500Zn(1)-O(2) 1.85 (2) C(4)-C(3)#2 1.25 (4) Zn(1)-O(1) 1.961 (13) C(4)-H(4)0.9500 Zn(2)-O(7) 1.857 (15) C(5)-C(6) 1.66 (3) Zn(2)-O(8) 1.859 (14)C(6)-C(8) 1.38 (3) Zn(2)-O(5) 1.864 (14) C(6)-C(7) 1.47 (3) Zn(2)-O(1)1.920 (7) C(7)-C(8)#3 1.29 (3) Zn(2)-Zn(3) 3.157 (3) C(7)-H(7) 0.9500Zn(3)-O(6)#1 1.853 (15) C(8)-C(7)#3 1.29 (3) Zn(3)-O(6) 1.853 (15)C(8)-H(8) 0.9500 Zn(3)-O(3) 1.864 (19) C(9)-C(10) 1.68 (3) Zn(3)-O(1)1.943 (14) C(10)-C(11) 1.45 (3) Zn(3)-Zn(2)#1 3.157 (3) C(10)-C(12) 1.45(3) O(1)-Zn(2)#1 1.920 (7) C(11)-C(12)#4 1.31 (3) O(2)-C(1) 1.22 (4)C(11)-H(11) 0.9500 O(3)-C(1) 1.33 (3) C(12)-C(11)#4 1.31 (3) O(4)-C(5)1.23 (2) C(12)-H(12) 0.9500 O(5)-C(5) 1.32 (2) C(13)-O(8)#1 1.291 (16)O(6)-C(9) 1.28 (2) C(13)-C(14) 1.68 (4) O(7)-C(9) 1.27 (2) C(14)-C(15)#11.43 (2) O(8)-C(13) 1.291 (16) C(14)-C(15) 1.43 (2) C(1)-C(2) 1.71 (4)C(15)-C(15)#5 1.26 (3) C(2)-C(4) 1.38 (4) C(15)-H(15) 0.9500 C(2)-C(3)1.44 (4) O(4)#1-Zn(1)-O(4) 106.5 (9) O(4)-Zn(1)-O(2) 106.3 (5)O(4)#1-Zn(1)-O(2) 106.3 (5) O(4)#1-Zn(1)-O(1) 111.9 (5) O(4)-Zn(1)-O(1)111.9 (5) Zn(2)-O(1)-Zn(3) 109.6 (5) O(2)-Zn(1)-O(1) 113.5 (7)Zn(2)#1-O(1)-Zn(1) 109.2 (5) O(7)-Zn(2)-O(8) 105.4 (6) Zn(2)-O(1)-Zn(1)109.2 (5) O(7)-Zn(2)-O(5) 105.9 (6) Zn(3)-O(1)-Zn(1) 108.3 (6)O(8)-Zn(2)-O(5) 106.7 (6) C(1)-O(2)-Zn(1) 126 (2) O(7)-Zn(2)-O(1) 113.0(6) C(1)-O(3)-Zn(3) 125 (2) O(8)-Zn(2)-O(1) 112.2 (5) C(5)-O(4)-Zn(1)128.2 (15) O(5)-Zn(2)-O(1) 113.0 (6) C(5)-O(5)-Zn(2) 124.8 (13)O(7)-Zn(2)-Zn(3) 77.6 (5) C(9)-O(6)-Zn(3) 124.1 (16) O(8)-Zn(2)-Zn(3)125.2 (4) C(9)-O(7)-Zn(2) 124.4 (15) O(5)-Zn(2)-Zn(3) 125.4 (4)C(13)-O(8)-Zn(2) 126.0 (16) O(1)-Zn(2)-Zn(3) 35.4 (4) O(2)-C(1)-O(3) 134(3) O(6)#1-Zn(3)-O(6) 106.4 (9) O(2)-C(1)-C(2) 118 (3) O(6)#1-Zn(3)-O(3)105.7 (6) O(3)-C(1)-C(2) 108 (3) O(6)-Zn(3)-O(3) 105.7 (6)C(4)-C(2)-C(3) 126 (3) O(6)#1-Zn(3)-O(1) 112.8 (5) C(4)-C(2)-C(1) 122(3) O(6)-Zn(3)-O(1) 112.8 (5) C(3)-C(2)-C(1) 112 (3) O(3)-Zn(3)-O(1)112.9 (8) C(4)#2-C(3)-C(2) 115 (4) O(6)#1-Zn(3)-Zn(2)#1 77.8 (5)C(4)#2-C(3)-H(3) 122.3 O(6)-Zn(3)-Zn(2)#1 126.2 (4) C(2)-C(3)-H(3) 122.3O(3)-Zn(3)-Zn(2)#1 125.1 (5) C(3)#2-C(4)-C(2) 118 (4) O(1)-Zn(3)-Zn(2)#134.95 (18) C(3)#2-C(4)-H(4) 120.9 O(6)#1-Zn(3)-Zn(2) 126.2 (4)C(2)-C(4)-H(4) 120.9 O(6)-Zn(3)-Zn(2) 77.8 (5) O(4)-C(5)-O(5) 133 (2)O(3)-Zn(3)-Zn(2) 125.1 (5) O(4)-C(5)-C(6) 119 (2) O(1)-Zn(3)-Zn(2) 34.95(18) O(5)-C(5)-C(6) 108.5 (18) Zn(2)#1-Zn(3)-Zn(2) 60.10 (9)C(8)-C(6)-C(7) 124 (2) Zn(2)#1-O(1)-Zn(2) 110.8 (6) C(8)-C(6)-C(5) 121(2) Zn(2)#1-O(1)-Zn(3) 109.6 (5) C(7)-C(6)-C(5) 115 (2) C(8)#3-C(7)-C(6)119 (2) C(10)-C(11)-H(11) 121.1 C(8)#3-C(7)-H(7) 120.3C(11)#4-C(12)-C(10) 116 (3) C(6)-C(7)-H(7) 120.3 C(11)#4-C(12)-H(12)122.1 C(7)#3-C(8)-C(6) 116 (2) C(10)-C(12)-H(12) 122.1 C(7)#3-C(8)-H(8)122.0 O(8)-C(13)-O(8)#1 133 (3) C(6)-C(8)-H(8) 122.0 O(8)-C(13)-C(14)113.6 (14) O(7)-C(9)-O(6) 136 (2) O(8)#1-C(13)-C(14) 113.6 (14)O(7)-C(9)-C(10) 112 (2) C(15)#1-C(14)-C(15) 127 (3) O(6)-C(9)-C(10) 112(2) C(15)#1-C(14)-C(13) 116.5 (14) C(11)-C(10)-C(12) 126 (2)C(15)-C(14)-C(13) 116.5 (14) C(11)-C(10)-C(9) 116 (2)C(15)#5-C(15)-C(14) 116.3 (14) C(12)-C(10)-C(9) 117 (2)C(15)#5-C(15)-H(15) 121.8 C(12)#4-C(11)-C(10) 118 (3) C(14)-C(15)-H(15)121.8 C(12)#4-C(11)-H(11) 121.1Symmetry Transformations Used to Generate Equivalent Atoms:

  #1 x, −y + 1, z #2 −x, −y + 1, −z #3 -x + ½, −y + ½, −z #4 −x + ½,−y + ½, −z + 1 #5 −x + 1, y, −z + 1

TABLE 16 Anisotropic displacement parameters (Å² × 10³) formvMOF-5-ACEF. U¹¹ U²² U³³ U²³ U¹³ U¹² Zn(1) 119 (3) 115 (3) 82 (2) 0 56(2) 0 Zn(2) 118 (2) 108 (2) 92 (2) 4 (1) 60 (2) 4 (1) Zn(3) 120 (3) 112(3) 93 (2) 0 65 (2) 0 The anisotropic displacement factor exponent takesthe form: −2π²[h² a*²U¹¹ + . . . + 2 h k a* b* U¹²]

TABLE 17 Hydrogen coordinates (×10⁴) and isotropic displacementparameters ( Å² × 10³) for ACEF. x y z U(eq) H(3) 448 5000 −692 283 H(4)430 5000 1575 270 H(7) 1964 3534 −701 283 H(8) 3092 2384 1608 278 H(11)3070 2374 4534 295 H(12) 1908 3525 4541 303 H(15) 4560 3847 4501 252

Porosity of mvMOFs, H₂ Uptake and CO₂ Separation Study.

All low-pressure gas adsorption experiments (up to 1 bar) were performedon a Quantachrome Autosorb-1 automatic volumetric instrument. A liquidnitrogen bath (77 K) and a liquid argon bath (87 K) were used for N₂, H₂and Ar, while a thermostated bath (273, 283, and 298 K) was used for theCO₂ and CO isotherm measurements. Ultra-high purity grade N₂, H₂, Ar,CO, He (99.999% purity) and CO₂ gases (99.995% purity) were usedthroughout the adsorption experiments. Non-ideality of gases wasobtained from the second virial coefficient at experimental temperature.For measurement of the apparent surface areas, the Langmuir method wasapplied using the adsorption branches of the N₂ (Ar) isotherms assuminga N₂ (Ar) cross-sectional area of 16.2 (14.2) A²/molecule.As-synthesized samples of MOFs were immersed in chloroform at ambienttemperature for three 24 h period, evacuated at ambient temperature for12 h.

The architectural rigidity and consequently the permanent porosity ofevacuated MOF-5, mvMOF-5-AB, -AI-a, -ABCD, and -ABCEFGHI wereunequivocally proven by gas-sorption analysis. Type I N₂/Ar adsorptionisotherm behavior was observed for these MOFs (FIGS. 45 and 46),revealing their microporous nature. The Langmuir surface area ofmvMOF-AB was calculated to be 3640 m²/g. Similarly, the apparent surfaceareas of MOF-5, mvMOF-5-AI-a, -ABCD, and -ABCEFGHI were calculated to be4140, 2680, 2860, and 1860 m²/g, respectively. In the MVMOF-5-AI series,as more bulky link I was introduced into crystal product, the calculateddensity increases from -a to -c, and surface area decreases (FIG. 48).

TABLE 18 Summary of porosity measurements for MOF-5, and mvMOFs. BETLangmuir Pore H₂ uptake Bulk SA SA volume at 760 torr density Compound(m²/g) (m²/g) (cm³/g) (cm³/g) (g/cm³) MOF-5 3320 4150 1.37 139 0.59mvMOF-5-AB 2980 3440 1.22 133 0.61 mvMOF-5-AC 2140 2580 0.92 122 0.66mvMOF-5-AD 1710 2110 0.75 101 0.65 mvMOF-5-AE 2490 3020 1.08 132 0.62mvMOF-5-AF 2400 2920 1.04 140 0.63 mvMOF-5-AG 2410 2860 1.02 139 0.63mvMOF-5-AH 2240 2760 0.98 172 0.67 mvMOF-5-AI-a 2230 2680 0.88 177 0.74mvMOF-5-AI-b 1500 1800 0.64 137 0.83 mvMOF-5-AI-c 1210 1440 0.51 1300.93 mvMOF-5-EI 1020 1210 0.43 1.02 mvMOF-5-AHI 1820 2210 0.79 189 0.81mvMOF-5-EHI 1176 1400 0.50 156 0.90 mvMOF-5-ABCD 2460 2860 1.00 0.69mvMOF-5-ACEF 1920 2400 0.83 0.65 mvMOF-5-ABCEFGHI 1640 1860 0.65 0.72

Pore size distribution analysis of mvMOF-5-AI and MOF-5. In addition,the pore size distribution of one of the mvMOF with bulky link wasstudied, MOF-5-AI-a. The fit of Ar adsorption isotherm for MOF-5-AI-awith a nonlocal density functional theory (NLDFT) model reveals that thepore size distribution is largely populated smaller than 12 Å, which isa typical pore size distribution of MOF-5 (FIG. 40). This indicates thatalmost all larger cages of MOF-5-AI-a are partially functionalized bylink I, no pore environment of MOF-5 exists.

CO₂ and CO adsorption isotherms for mvMOF-5-EI are illustrated in FIGS.47-50, respectively. To estimate reliable Henry's constants, avirial-type expression comprising the temperature-independent parametersa, and b, was applied:

$\begin{matrix}{{\ln\mspace{14mu} P} = {{\ln\mspace{14mu} N} + {\frac{1}{T}{\sum\limits_{i = 0}^{m}{a_{i}N^{i}}}} + {\sum\limits_{i = 0}^{n}{b_{i}N^{i}}}}} & (1)\end{matrix}$where P is pressure, N is the adsorbed amount, T is temperature, and mand n represent the number of coefficients required to adequatelydescribe the isotherms. From these results, the Henry's constant (K_(H))is calculated from where T is temperature.K _(H)=exp(−b ₀)·exp(−a ₀ /T)  (2)The Henry's Law selectivity for gas component i over j at 298 K iscalculated based on eq. (3).S _(ij) =K _(Hi) /K _(Hj)  (3)

A number of embodiments of the invention have been described.Nevertheless, it will be understood that various modifications may bemade without departing from the spirit and scope of the invention.Accordingly, other embodiments are within the scope of the followingclaims.

What is claimed is:
 1. A porous multi-variate metal organic framework(mvMOF) comprising a plurality of linking moieties wherein one or morelinking moieties have a general structure selected from the groupconsisting of

wherein functional groups R₁-R₄ are selected from the group consistingof —H, —NH₂, —BR, —Cl, —NO₂, —CH₃, —OCH₂R₅, and —O—CH₂R₆, wherein R₅ isan alkyl or alkene of from about 1-5 carbons, and R₆ is an aryl orsubstitute aryl, or wherein R₁-R₂ when adjacent can form a ring andwherein the functional groups between at least two or more linkingmoieties are non-uniform, and wherein the functional groups of one ormore linking moieties do not adversely affect the connectivity orspatial orientation of the linking clusters to one or more metals ormetal ions, and wherein the functional groups modify the chemical andphysical properties of a pore in the framework.
 2. The mvMOF of claim 1,wherein the mvMOF is constructed of three or more linking moieties thathave non-uniform functional groups.
 3. The mvMOF of claim 1, wherein themvMOF comprises repeating units of one or more linking moieties joinedto one or more metal or metal ions through one or more linking clusters,and a plurality of functional groups which are covalently bound to thelinking moieties, wherein the functional groups are heterogeneous and/orwherein the functional groups are positional isomers.
 4. The mvMOF ofclaim 1, wherein each of the pores within the framework comprise aplurality of different functional groups pointing into the center of apore.
 5. The mvMOF of claim 1, wherein the framework comprises atopology of a MOF-5 framework.
 6. The mvMOF of claim 1, wherein theframework comprise a metal ion selected from the group consisting of:Li⁺, Na⁺, Rb⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sc³⁺, Ti⁴⁺, Zr⁴⁺, Ta³⁺, Cr³⁺,Mo³⁺, W³⁺, Mn³⁺, Fe³⁺, Fe²⁺, Ru³⁺, Ru²⁺, Os³⁺, Os²⁺, Co³⁺, Co²⁺, Ni²⁺,Ni⁺, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Au⁺, Zn²⁺, Al³⁺, Ga³⁺, In³⁺, Si⁴⁺,Si²⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺, Sn²⁺, Bi⁵⁺, Bi³⁺, and combinations thereof,along with corresponding metal salt counter-anions.
 7. The mvMOF ofclaim 1, wherein the linking moiety comprises a structure selected fromthe group consisting of:


8. The mvMOF of claim 1, wherein one or more functional groups of one ormore linking moieties can be (1) selectively reacted with apost-framework reactant so as to add to, eliminate, or substitute atleast one functional group of one or more linking moieties, but whereinat least one other functional group of a linking moiety does not reactwith the post-framework reactant, and wherein (1) is repeated from 0 to10 times.
 9. The mvMOF of claim 1, made by a process comprising mixing aplurality of chemically functionalized linking moieties with a metal ionor metal containing salt, wherein the linking moieties are at a desiredratio to incorporate the desired ratio of a particular combination oflinking moieties into the organic framework, purifying the crystals andremoving the solvent.
 10. The mvMOF of claim 9, wherein the methodcomprises mixing a plurality of chemically functionalized linkingmoieties at desired ratios to incorporate the desired ratio of aparticular combination of linking moieties into an organic frameworkcomprising benzenedicarboxylic acid with zinc nitrate in DEF/DMF.
 11. Agas separation device comprising the mvMOF of claim
 1. 12. A gas storagedevice comprising the mvMOF of claim
 1. 13. The mvMOF of claim 1,wherein the mvMOF comprises improved gas sorption capacity compared to aMOF having the same topology but homogenous linking moieties.
 14. ThemvMOF of claim 1, wherein one or more functional groups and/or one ormore post-framework reactants modifies at least one property of themvMOF framework selected from the group consisting of: modulates the gasstorage ability of the mvMOF framework; modulates the sorptionproperties of the mvMOF framework; modulates the pore size of the mvMOFframework; modulates the catalytic activity of the mvMOF framework;modulates the conductivity of the mvMOF framework; and modulates thesensitivity of the mvMOF framework to the presence of an analyte ofinterest.
 15. The mvMOF of claim 14, wherein one or more functionalgroups and/or one or more post-framework reactants modifies at least twoproperties of the mvMOF framework selected from the group consisting of:modulates the gas storage ability of the mvMOF framework; modulates thesorption properties of the mvMOF framework; modulates the pore size ofthe mvMOF framework; modulates the catalytic activity of the mvMOFframework; modulates the conductivity of the mvMOF framework; andmodulates the sensitivity of the mvMOF framework to the presence of ananalyte of interest.
 16. The mvMOF of claim 5, wherein the frameworkcomprising a topology of a MOF-5 framework is selected from the groupconsisting of mvMOF-5-AB, -AC, -AD, -AE, -AF, -AG, -AH, -AI, -EI, -ABC,-AHI, -EHI, -ABCD, -ACEF, -ABCHI, -ABCGHI, -ABCEFHI, and -ABCEFGHI. 17.The process of claim 9, wherein the chemically functionalized linkingmoieties results from reacting a linking moiety comprising carboxylicacid-based linking clusters with one or more functionalizing reagents,and wherein the carboxylic acid-based linking clusters may or may not befirst protected with a protecting group prior to reacting with one ormore functionalization reagents and then may or may not be de-protectedprior to mixing with a metal ion or metal containing salt.
 18. Theprocess of claim 9, wherein the chemically functionalized linkingmoieties results from reacting terephthalic acid with one or morefunctionalizing reagents.
 19. A porous mvMOF comprising a plurality oflinking moieties comprising one or more functional groups, wherein thefunctional groups between at least two or more linking moieties arenon-uniform, and wherein the functional groups of one or more linkingmoieties do not adversely affect the connectivity or spatial orientationof the linking clusters to one or more metals or metal ions, and whereinthe functional groups modify the chemical and physical properties of apore in the framework.
 20. The mvMOF of claim 19, wherein the linkingmoieties are comprised of organic parent chains selected from the groupconsisting of one or more optionally substituted aryls, heterocycles,cycloalkyls, cylcoalkenyls, or combinations thereof, and one or morelinking clusters.